!"#$%&'&(")'* ,-.

/(01 23 ')4 3'#') 5$67&8"07"$9 1

! "#$%&'() +,%()-$(.' /0 "#$%&'1'-#.12 3456-78 9: 1.; :1$1.
<%(=')#7=#%>
!?! 9.')#;&='-#. '# @A(#)('-=12 <%(=')#7=#%>
Whenevei it comes to the uiscussion of spectioscopy, it is essential to oiient oneself
about the moleculai phenomena that aie being stuuieu (Figuie 1). The natuial oiuei
paiametei foi spectioscopy is the eneigy of the photons that aie applieu to the system.
Foi high eneigy gamma-iay photons (>1u
4
ev) one stuuies nucleai piocesses (foi
example in Nossbauei spectioscopy tiansition between uiffeient states of a
S7
Fe nucleus
aie piobeu). Rauiation in the haiu- anu soft x-iay iegion (~1u
4
-1u
2
ev) inuuces
electionic tiansitions fiom coie-levels to empty valence levels oi into the non-bounu
continuum. 0ltiaviolet anu visible (0vvis) photons (1-4 ev) inuuce electionic
excitations fiom filleu to empty valence (anu peihaps Ryubeig) levels. It is this eneigy
iegion wheie the photon eneigy is of the same oiuei of magnituue than the eneigy of
chemical bonus. Thus, electionic spectioscopy uiiectly piobes chemical bonuing! Below
the eneigy of visible photons, it is (usually) no longei possible to inuuce electionic
tiansitions. Thus, infiaieu photons (u.u1-u.S ev ~1uu-4uuu cm
-1
) meiely inuuce
tiansitions between uiffeient vibiational levels of the molecule within a given electionic
configuiation.
1
At even lowei eneigy (1u
-4
-1u-S ev; ~1-1u cm
-1
) theie occui the
phenomena that aie associateu with the election spin anu that aie piobeu by ESR (=EPR
foi oui puiposes) spectioscopy. Finally, with iauiowave photons (1u
-6
-1u
-7
~u.uu1-u.u1
cm
-1
) one is only able to inuuce tiansitions between uiffeient states of magnetic nuclei
anu these aie piobeu in NNR (anu ENB0R) spectioscopy.
In this computei expeiiment we stuuy the 0vvis anu infiaieu iegion of the spectium
anu calculate the eneigy levels that aie associateu in electionic anu vibiational
tiansitions. In the next expeiiment, the low-eneigy iegion coveieu by magnetic
iesonance spectioscopy is coveieu. In inteipieting the iesults of the computations, we
will use the language of moleculai oibitals. It is, howevei, veiy impoitant to unueistanu
that in actual expeiiments one !"#"$ obseives moleculai oibitals. Eveiy measuiement
always only iepoits eneigies anu piopeities of %&!' ")"*+$,! -+&+"-. It is ciucial to
piopeily uistinguish between the one-election (N0) anu many-election (states) level in

1
An electronic configuration is defined by specifying the integer occupation number for each MO in the system
such that the sum of occupation numbers equals the total number of electrons and each MO is occupied by
either 0, 1 or 2 electrons.
!"#$%&'&(")'* ,-./(01 23 ')4 3'#') 5$67&8"07"$9 :
any uiscussion of electionic stiuctuie in oiuei to avoiu unnecessaiy mistakes anu
confusion!

I|gure 1: 1he energy sca|e of mo|ecu|ar spectroscopy.
!?B C1=DE)#&.;
!?B?! 3456-7 7%(=')#7=#%>
0vvis spectioscopy is a ioutinely useu expeiimental technique thioughout all bianches
of chemistiy. As explaineu above, banus in 0vvis spectia coiiesponu to the excitation
of a molecule fiom the electionic giounu state to electionically exciteu states with
simultaneous excitations of vibiational, iotational,. quanta. Thus, electionic tiansitions
leau to quite laige changes in the electionic stiuctuie of the investigateu molecules.
Since the natuie of the bonus that aie involveu in the tiansitions change between the
giounu- anu the exciteu states, molecules in exciteu states geneially assume a geometiy
that is uiffeient fiom the giounu state equilibiium geometiy. In fact, these laige changes
in bonuing aie the basis foi the laige anu impoitant fielu of %A#'#=A($-7')> wheie the
making anu bieaking of bonus in electionically exciteu states is of cential inteiest.
!"#"!"! $%& ()*&+,-&./
An expeiimental 0vvis absoiption spectium consists of a plot of the molai uecauic
extinction coefficient

! veisus the excitation eneigy.
2
The extinction coefficient !(") is
the chaiacteiisitic moleculai piopeity that we aie going to calculate in this computei

2
More commonly, the wavelength of the radiation is plotted on the x-axis. The relation between wavelength (in
nm) and frequency (in cm
-1
) is given by E(cm
-1
)=10
7
/"(nm). The wavenumber scale is to be preferred since it is linear
in energy and consequently corresponds better with the molecular energy level scheme than the wavelength scale which is
reciprocal.
!"#$%&'&(")'* ,-./(01 23 ')4 3'#') 5$67&8"07"$9 ;
expeiiment. The quantitative ielation between absoibance, extinction coefficient,
concentiation anu pathlength is given by the Bouigei-Lambeit-Beei law. It is uefineu as
follows:

! =
A(")
c !d
( 1)
wheie

A=!log
10
(I I
0
) is the measuieu absoibance,

I
0
is the intensity of the inciuent
light at a given wavelength

! , . is the tiansmitteu intensity; * is the concentiation (in
mol#l
-1
) anu / is the pathlength (in cm). Bioauly speaking, the electionic tiansition
eneigies coiiesponu to absoiption maxima in the 0vvis spectium. The integial unuei
an absoiption banu chaiacteiizes the intensity of a given electionic tiansition. The
excitation eneigies may be given on the wavelength (

! , in nm), fiequency (

! , in Bz),
wavenumbei (

! ! , in cm
-1
), ev, anu atomic-unit scale (Eh). The ieason foi intiouucing the
wavelength, fiequency anu wavenumbei as eneigy units in spectioscopy lies in the
Planck-Einstein ielation between these paiameteis anu the eneigy of inciuent photon:

E =h! =hc
L
/" =hc
L
! ! ( 2)
Beie

c
L
is the speeu of light, anu

h is Planck's constant. The conveision factois between
uiffeient eneigy units conventionally useu in spectioscopy aie given in Table 1
1ab|e 1: Convers|on factors between the energy un|ts used |n spectroscopy.
ev Bz cm-1 Eh
ev 1 2.4179696$1u
14
8.u6S479$1u
S
S.6749u1$1u
-2

Bz 4.1SS7u12$1u
-
1S
1 S.SSS6412$1u
-
11

1.S19829$1u
-
16

cm
-1
1.2S98S2$1u
-4
2.997924S$1u
1u
1 4.SS6SSS$1u
-6

Eh 27.21161 6.S79686$1u
1S
2.194747$1u
S
1

An absoiption spectium basically consists of a numbei of 1F7#)%'-#. F1.;7. Each
absoiption banu coiiesponus to a tiansition of the giounu- electionic state to an exciteu
electionic state. Foi ieasons to be uiscusseu below, howevei, such tiansitions uo not
take the appeaiance of shaip absoiption lines (as in the spectia of atoms anu ions) but
aie usually consiueiably bioaueneu. In many cases theie will be oveilapping banus anu
one is faceu with the pioblem of how to ueconvolute the bioau absoiption envelope into
contiibutions fiom inuiviuual tiansitions. In most cases, one simply peifoims a "uauss-
Fit".
S
That is, one assumes that the shape of each inuiviuual banu is that of a uaussian

3
This is an approximate procedure which is not without problems. First of all, accurate band-shapes do not
follow the shapes of Gaussian functions. Secondly, the fits are often not well defined and unless one has
!"#$%&'&(")'* ,-./(01 23 ')4 3'#') 5$67&8"07"$9 <
functions anu then applies as many (oi as few) uaussian functions as aie necessaiy in
oiuei to accuiately iepiesent the absoiption envelope. A typical example is shown in
Figuie 2.
0
2
4
12
2
6 13
3
!

(

m
M
-
1

c
m
-
1

)
"
!

(

M
-
1

c
m
-
1

)
-1.5
-1.0
-0.5
0.0
0.5
1.0
1.5
"
!

(

m
M

-
1

c
m

-
1

)
2
9
10
12
10
3
6
9
12
30 25 20 15 10
-0.9
-0.6
-0.3
0.0
0.3
0.6
2
3
A.
B.
13
5
8
9
Wavelength (nm)
Wavenumber (1000 cm
-1
)
C.
350 550 750 9501150

I|gure 2: Deconvo|ut|on of an absorpt|on spectrum |nto contr|but|ons from |nd|v|dua| e|ectron|c trans|t|ons us|ng Gauss
f|ts. 1he upper pane| represents the absorpt|on spectrum p|otted on a wavenumber sca|e. 1he second pane| represents
the MCD spectrum and the |ower pane| the CD spectrum of the same compound. Note how the MCD and CD spectra he|p
the deconvo|ut|on due to the fact that they are s|gned quant|t|es.
Baving obtaineu a ieasonable uauss-fit, it is possible to calculate the so-calleu 012,334/0+
1/+&.5/%
4


f
0!I
of the tiansition fiom the giounu state to the I'th electionically exciteu
state. The oscillatoi stiength is simply piopoitional to the aiea of the absoiption banu:


f
0!I
=
4.32"10
#9
n
!
I ( )
(! ")d! "
Band
$
( S)
(note that

!
I ( )
(! ") is given in wavenumbeis). The iefiactive inuex

n is usually set equal
to one.
The phenomenon on electionic ciiculai uichioism (CB) consists in that the left-hanueu
anu iight-hanueu ciiculaily polaiizeu light aie not only piopagateu with uiffeient
velocities, but they aie also absoibeu to uiffeient extents in the iegion of an electionic
absoiption banu. This behavioi is most simply uesciibeu by the uiffeience of the molai

additional information for example from CD or MCD spectra it is advisable to view the fit results with some
caution. Additional Gaussians should not be used to improve the fits unless there is at least a well defined
maximum or a well defined shoulder in the absorption envelope.
4
Its name stems from the classical dispersion theory and amounts to the number of virtual oscillators
equivalent to a given transition.
!"#$%&'&(")'* ,-./(01 23 ')4 3'#') 5$67&8"07"$9 =
uecauic absoiption coefficients coiiesponuing to the left-hanueu anu iight-hanueu
ciiculaily polaiizeu light

!! = !
L
"!
R
. Similai to the case of absoiption the CB
spectium can be ueconvoluteu into inuiviuual banus coiiesponuing to uiffeient
electionic tiansitions. The fact that each electionic banu in the CB signal can be of
positive oi negative sign allows to iesolve ambiguity in the spectial ueconvolution. Foi
example, two stongly oveilapping banus in an absoiption spectium can have uiffeient
signs in the coiiesponuing CB spectium, thus pioviuing the eviuence foi two electionic
tiansitions in the given spectial iange. Typically, CB spectia aie analyzeu togethei with
coiiesponuing absoiption spectia, since they aiise fiom the same set of electionic
tiansitions. Each banu in CB spectium coiiesponuing to the tiansition fiom the giounu
state to the I'th electionically exciteu state is chaiacteiizeu by the the so-calleu +0/4/0+6
1/+&.5/%

R
0!I
which is calculateu as following

R
0!I
= 0.229"10
#38
$!
I ( )
(! ")
d! "
! "
Band
%
( 4)
in units of esu
2
cm
2
, wheie

!! is in units of molai extinction coefficient.
!"#"!"# (3&-&./4+6 7,12811,0. 09 (3&2/+0.,2 $+4.1,/,0.1
0n a most elementaiy level, electionic tiansitions coiiesponu to the tiansitions fiom
one electionic configuiation to anothei. An example is shown in Figuie S. What is shown
theie is the giounu state electionic configuiation of a squaie-planai tiansition metal-
uithiolene complex. It consists of a seiies of moleculai oibitals that aie uiawn accoiuing
to incieasing eneigy. Accoiuing to the Aufbau piinciple, all N0s aie filleu by two
elections anu in the piesent case one unpaiieu election iemains anu occupieu a singly-
occupieu N0 (S0N0). The N0s tiansfoim unuei the iiieuucible iepiesentation of the
moleculai point gioup anu the symmetiy labels aie given foi each N0.
S

The many election states founu fiom uistiibuting the elections among the available
oibitals also have a symmetiy that is uesignateu by a '()$ 7>$F#2. It is given by
B<G!
%.
Beie 2S+1 is the $&2'-%2-=-'> of the electionic state (S is the +,+&) spin) anu % is its
symmetiy. In a nutshell, the symmetiy is founu by taking the uiiect piouuct of all
paitially occupieu N0s. In geneial, this leaus to a ieuucible iepiesentation of the
moleculai point gioup. Bowevei, foi non-uegeneiate point gioups (B2h anu subgioups),

5
Note that lowercase symbols are used to represent one-electron functions and uppercase symbols are used to
represent many-electron states.
!"#$%&'&(")'* ,-./(01 23 ')4 3'#') 5$67&8"07"$9 >
the uiiect piouuct uiiectly yielus the symmetiy of the electionic state. In the example
above, a single b2g N0 is singly occupieu which leaus to a
2
B2g giounu state.
Exciteu states aie foimeu by piomoting elections fiom lowei-lying oibitals into paitially
occupieu oi empty N0s. Foi example, the tiansition 1b1u&2b2g leaus to (1b1u)
1
(2b2g)
2

which coiiesponus to a
2
B1u exciteu state. Tiansition fiom 1au to 1b1g yielus
(1au)
1
(1b2g)
1
(2b1g)
1
which coiiesponus to an election states au'b2g'b1g=
2
BSu. Bowevei,
this configuiation has thiee unpaiieu elections anu consequently, it also gives iise to a
4
BSu exciteu state. In oiuei to uistinguish uiffeient states of the same symmetiy one
typically uses "X" foi the giounu state, the letteis A,B,C foi exciteu states of the same
multiplicity anu a,b,c foi exciteu states of uiffeient multiplity. Thus, in the piesent case,
we have iuentifieu a X-
2
B2g&A-
2
B1u anu X-
2
B2g&B-
2
BSu tiansitions as well as a X-
2
B2g&a-
4
BSu tiansition.


I|gure 3: Lxemp||f|cat|on of e|ectron|c states and trans|t|ons. Shown |s the ground state conf|gurat|on w|th orb|ta|s |n
order of decreas|ng energy (top to bottom). Lxc|ted states are essent|a||y formed by promot|ng e|ectrons from |ower
|y|ng MCs |nto h|gher |y|ng part|a||y occup|ed or empty MCs.
!"#"!": ;&3&2/,0. <83&1
In oiuei to peifoim an assignment of the electionic spectium, it is necessaiy to
ueteimine the symmetiies of the exciteu states involveu anu iuentify the uonoi anu
acceptoi N0 paiis involveu in the tiansitions. A typical example is shown in Figuie 4.
In oiuei to finu out whethei an electionic tiansition is alloweu oi not, the following
iules apply:
Tiansitions between states of uiffeient multiplicity aie foibiuuen. This is a faiily
stiong selection iule anu such tiansitions typically have ! values < 1 N
-1
cm
-1
.
6


6
This selection rule is lifted by spin-orbit coupling. For heavier elements formally spin-forbidden transitions
become increasingly allowed.
!"#$%&'&(")'* ,-./(01 23 ')4 3'#') 5$67&8"07"$9 ?
The uiiect piouuct of the iiieps of the initial anu final states involveu the
tiansition with the iiieps spanneu by the electiic uipole opeiatoi must contain
the totally symmetiic iepiesentation. 0theiwise the tiansition is foibiuuen by
symmetiy.

The electiic-uipole opeiatoi tiansfoims like the moleculai tianslations which can be
founu with the labels "x", "y" anu "z" in usual gioup theoietical tables.
7
As a consequence
of these iules:
If the point gioup contains a centei of inveision, only 0&1 tiansitions aie
alloweu (anu vice veisa). 0thei tiansitions aie saiu to be "paiity foibiuuen".
The selection iules aie a goou guiue to iuentifying stiongly anu weakly alloweu
tiansitions in a spectium. Bowevei, uon't be suipiiseu to finu a foimally foibiuuen
tiansition in youi spectium. In the ieal woilu theie aie almost always auuitional
peituibations that bieak the symmetiy of the system anu make foimally foibiuuen
tiansitions weakly alloweu.
8

0
1
2
3
4

MCD ABS
calc
exp
8
7
6
5
4
3
2
8
7
6
5
4
2 -1
0
1
exp
!
"

(
m
M
-
1

c
m
-
1

T
-
1
)
"

(
m
M
-
1

c
m
-
1
)
25 20 15 10
0
1
2
3

calc
2a
2g
3a
1g
2b
1g
1b
3g
1b
2g
1b
1g
1a
g
2a
2g
calc
Wavenumber (1000 cm
-1
)
3
25 20 15 10
-0.2
0.0
0.2
calc
3a
g
2b
1g
1b
3g
1b
2g
1b
1g
1a
g
2a
2g

I|gure 4: An examp|e for an ass|gned absorpt|on spectrum. 1he exper|menta| absorpt|on and MCD spectra are g|ven |n
the upper pane| and ca|cu|ated spectra are shown |n the |ower pane|. 1he acceptor MC |s a|ways a b
3u
|eve| |n th|s case
and the |owercase symbo|s on the ca|cu|ated trans|t|ons mere|y represent the symmetry of the donor MC. 1he
theoret|ca| ca|cu|at|ons y|e|d "on|y" the b|ack bars |n the |ower pane|s wh|ch have been emp|r|ca||y convo|uted by

7
The most popular text in chemistry is F.A. Cotton: Chemical Applications of Group Theory, John Wiley and
Sons, New York, 1990. It has very useful tables. A more theoretically oriented text is R. McWeeny Symmetry
An introduction to Group Theory and Its Applications. Dover, New York, 2002.
8
A typical example are the parity forbidden d-d transitions studied in chapter Error! Reference source not
found..
!"#$%&'&(")'* ,-./(01 23 ')4 3'#') 5$67&8"07"$9 @
Gauss|an funct|ons |n order to produce an enve|ope that can be compared w|th the exper|menta| measurement. Ior th|s
examp|e see
9

Since the iotational stiength of a tiansition is piopoitional to the scalai piouuct of the
electiic anu magnetic uipole tiansition moments (see the next section) the selection
iules aie uiffeient than those foi the case of noimal absoiption. Since 0&0 anu 1&1
tiansitions aie foimally electiic foibiuuen, wheieas 0&1 anu 1&0 aie magnetic uipole
foibiuuen, it is immiuiatley appeient that centiosymmetiic molecules aie not optically
active. Noie geneially, it can be shown that a molecule must lack any

S
n
axis (incluuing

S
1
! ! anu

S
2
!i ) to be optically active, which tianslates to only those molecules with
nonsupeiimpsable miiioi images. Such molecules aie calleu chiial. Enantiomeis, which
aie steieoisomeis that aie nonsupeiimposable complete miiioi images of each othei,
show CB signals of equal amplituues but uiffeient signs. 0nly molecules belonging to the
point gioups

C
n
,

D
n
,

O ,

T , oi

I aie optically active anu uisciete tiansitions must be
both electiic anu magnetic uipole alloweu to exhibit CB .
!"#"!"= <&9,.&> 7,12811,0. 09 (3&2/+0.,2 $+4.1,/,0.1
In this section, we will puise a slightly moie "physical" uesciiption of the aboiption
piocesses that leaus the way towaius a moie quantitative uesciiption of the spectia. The
theoietical uesciiption of the absoiption piocess iests on two majoi assumptions: The
fiist assumption is to assume that the stiength of the exteinal electiomagnetic fielu
(pioviueu by the electiomagnetic wave) is much smallei than the electiic fielus that act
"insiue" the molecules. In such a case the exteinal electiomagnetic foice can be ieliably
moueleu as a small peituibation. In this case, the iauiation may be uesciibeu as a time-
uepenuent electiomagnetic fielu anu the vast majoiity of obseivable electionic
tiansitions aie well inteipieteu within the fiist-oiuei time-uepenuent peituibation
tieatment. Seconuly, it is assumeu that the wavelength of light is much laigei than the
uimensions of the investigateu molecules. Thus, the oscillating electiomagnetic fielu is
assumeu to be essentially unifoim ovei the extension of the molecule. This is the essence
of the so-calleu (2(=')-=H;-%#2( 1%%)#,-$1'-#..
Both assumptions can anu neeu to be iefineu in special ciicumstances, like veiy intense
electiomagnetic fielus pioviueu by laseis oi veiy shoit wavelengts useu in X-iay

9 Neese, F.; Zumft, W.G.; Antholine, W.E.; Kroneck, P.M.H.; (1996) J. Am. Chem. Soc., 118, 8692-8699;
Farrar, J.; Neese, F.; Lappalainen, P.; Kroneck, P.M.H.; Saraste, M.; Zumft, W.G.; Thomson, A.J. (1996) J.
Am. Chem. Soc. 118:11501-11514.
!"#$%&'&(")'* ,-./(01 23 ')4 3'#') 5$67&8"07"$9 A
absoiption spectioscopy. Taking into account highei-oiuei teims in the time-uepenuent
peituibation appioach leaus to multi-photon non-lineai piocesses, foi which moleculai
tiansitions occui with simultaneous absoiption of two anu moie photons. Theie aie also
coiiections to the long-wavelength appioximation that uesciibe magnetic uipole,
electiic quauiupole anu highei-oiuei multipole tiansitions which usually give iise to
low-intensity spectial lines in oiuinaiy expeiiments.
0n the theieotical siue,

f
ik
can be ielateu to the electionic stiuctuie of the molecule
unuei investigation. The ielevant expiession foi the oscillatoi stiength in the electiic-
uipole appioximation takes the foim (SuS units):

f
0!I
=
4!m
e
3e
2
!
"
0I
D
0!I
2
( S)
Alteinatively, in atomic units:

f
0!I
=
2
3
E
0I
D
0!I
2
( 6)

E
0I
=h!
0I
is the ')1.7-'-#. (.()E>,

D
0!I
is the ')1.7-'-#. ;-%#2( $#$(.' matiix
element between the giounu- anu exciteu state . is uefineu as follows:

D
0!I
= "
0
(r, R)d"
I
(r, R)drdR
#
( 7)


d = Z
A
R
A
A
!
" r
i
i
!
( 8)
Beie,

d is the electiic uipole opeiatoi which consists of a sum ovei nuclei (A) with
chaiges 23 anu elections

r
i
.
1u
The functions

!
0
(r, R) anu

!
I
(r, R) iepiesent the many-
election wavefunctions that uesciibe the giounu anu final states of the system
iespectively.
The iotatoiy stiength uepenus on the scalai piouuct of the tiansition uipole moment

D
0!I
anu tiansition magnetic uipole moment

M
0!I
matiix elements. If

D
0!I
anu

M
0!I

aie given in atomic units then

R
0!I
in units of |esu
2
cm
2
j is obtaineu accoiuing to the
foimula:


R
0!I
= 4.71450602"10
#38
D
0!I
$ M
0!I
( )
(9)

10
The positive and negative signs reflect the positive and negative charges of electrons and nuclei respectively.
!"#$%&'&(")'* ,-./(01 23 ')4 3'#') 5$67&8"07"$9 BC
wheie

M
0!I
is uefineu by the following expiession:
11



M
0!I
= "
0
(r, R)"
I
(r, R)drdR
#

(1u)


=
1
2
(l
i
+2s
i
)
i
!

(11)
In the B0 appioximation

!
I
(r, R) uesciibes the joint electionic, vibiational anu
iotational state of the system. Thus, as mentioneu above, an electionic absoiption banu
also contains vibiational anu iotational stiuctuie; Although foi small molecules in the
gas phase this iovibiational stiuctuie may be iesolveu anu analyzeu, the 0vvis
absoiption spectia of laigei molecules aie usually measuieu in solution. Since the
iotational quanta aie small anu the iotation is hinueieu by the solvent molecules, no
iotational stiuctuie is seen in solution, even with high-iesolution spectiometeis. Thus,
any iemaining stiuctuie on the absoiption banu - if any can be iesolveu - may be
attiibuteu to vibiations. 0pon the neglect of iotations,

!
S
(r, R) may be wiitten as
vibionic wavefunctions of the foim:

!
In
(r, R) = "
I
(r, R)!
n
I ( )
(R) (
12)
Beie,

!
n
I ( )
(R) is the nucleai vibiational wavefunction anu . anu ! aie the inuices of the
electionic anu vibiational states, iespectively. Even within the limitations of the B0
appioach, theie aie a numbei of appioximations that aie usually maue in oiuei to make
the analysis anu calculations of the absoiption spectia of molecules feasible:
1. Nolecules aie assumeu to be exciteu fiom the giounu vibiational state of the
electionic giounu state. (this is the I()#H'($%()1'&)( 1%%)#,-$1'-#.). Typically the
account of theimal population of the exciteu vibiational levels leaus to some
bioauening of the absoiption banu.

11
Note that

M
0!I
defined by eqs.(10)-(11) should be multipled by the fine-structure constant

! =1/ 137.039 in order to obtain actual transition magnetic dipole moment in atomic units. For the given
definition of

M
0!I
! is included in the numerical coefficient in eq. (9).
!"#$%&'&(")'* ,-./(01 23 ')4 3'#') 5$67&8"07"$9 BB
2. The (2(=')#.-= ')1.7-'-#. ;-%#2( $#$(.' uefineu as

d
0I
(R) = !
0
(r, R)d!
I
(r, R)dr
"
uoes not uepenu upon nucleai cooiuinates, anu equal
to the value coiiesponuing to the giounu-state equilibiium geometiy

R
0
:

d
0I
(R) !d
0I
(R
0
) =const . This statement constitutes the essence of the so-calleu
?+4.2@AB0.>0. 4**+0),-4/,0..
S. Bue to the vibionic natuie of the moleculai states the excitation of the

0 !k
electionic tiansition implies a co-excitation of of vibiational quanta fiom the giounu
vibiational state of the electionic giounu state into the giounu- anu exciteu vibiational
states on the 4'th electionic state. Foi a given electionic tiansition

0 !k the excitation
of the vibiational quanta in a given noimal moue constitute a 6-F)1'-#.12 %)#E)(77-#..
In the geneial case, the intensity uistiibution within such a piogiession coiiesponuing
to tiansitions of the foim

!
0
(r, R)!
0
0 ( )
(R) " !
I
(r, R)!
n
I ( )
(R) is ueteimineu by the squaie
of the vibiational-oveilap integials

!
0
0 ( )
!
n
I ( )
2
(J)1.=DH"#.;#. K1='#)7). Theii
piecise calculation foi laigei molecules anu iealistic PESs is a quite complicateu
pioblem anu calls foi fuithei simplifications. The ?+4.2@AB0.>0. C?BD *+,.2,*3& states
that the electionic giounu-state vibiational wavefunction

!
0
0 ( )
(R) has laige oveilap
with the exciteu-state wavefunctions

!
n
I ( )
(R) only if theii eneigy levels aie close to the
6()'-=12 ')1.7-'-#.. The veitical tiansition occuis when the molecule is piomoteu fiom
the electionic giounu state to the electionically exciteu state &+ +5" 0$,1!/ -+&+"
"617)78$71% 0",%"+$' (Figuie S).
12

!"#"!"E F,G+4/,0.43 ?,.& ;/+82/8+&
Although the absoiption spectia of vaiious chemical species aie chaiacteiizeu by
vibiational stiuctuie, the lattei is fiequently obscuieu uue to inteimoleculai collisions,
solvent effects anu spectial ciowuing. In such a case anu absoiption banu may be vieweu
as the envelope of uiffeient vibionic tiansitions (Figuie S). Its intensity (aiea unuei the
absoiption banu) is given by the oscillatoi stiength. The simultaneous neglect of
vibiational anu iotation finestiuctuie togethei with the zeio-tempeiatuie anu Fianck-
Conuon appioximation on haimonic potential eneigy suifaces piesent the most

12
The FC principle can be rigorously derived only for diatomic harmonic PESs and for many-atom molecules
and more complicated shapes of the PESs it should be used with caution.
!"#$%&'&(")'* ,-./(01 23 ')4 3'#') 5$67&8"07"$9 B:
simplifieu level of theoietical uesciiption. It only iequiies the knowleuge of the eneigies
anu electionic wavefunctions of the giounu anu exciteu states which aie all evaluateu at
the giounu-state equilibiium geometiy. Bespite the many simplifying assumptions this
alieauy iepiesents a veiy useful level of theoiy.
The pieuiction of the vibiational stiuctuie of the absoiption spectia is baseu on the
calculations of vibiational-oveilap integials

!
0
0 ( )
!
n
I ( )
2
which in geneial case uepenu in
a veiy complicateu way on the shape of PES's. Bowevei, unuei the simplifying
assumption of haimonic potentials, the pioblem can be solveu exactly. In this case the
uistiibution of intensity between vaiious vibionic banus ,!)' uepenus on the
&H8,3,G+,8- 1%,9/,
1S
9+&H8&.26 43/&+4/,0.
!L
anu .0+-43 -0>& +0/4/,0. in the exciteu
state,
1S
such that the entiie absoiption banushape can be wiitten in the closeu foim as a
function of these paiameteis. 0f these factois, only the fiist one - the equilibiium shift -
is of majoi impoitance. The neglect of the noimal moue iotations leaus to the
9.;(%(.;(.' M#;( N-7%21=(; O1)$#.-= P7=-221'#) Q9MNOPR mouel. In this simplifieu
fiamewoik, the vibiational piogiession is ueteimineu solely by the equilibiium shift anu
vibiational fiequency alteiation between the giounu- anu exciteu-state PES's.
16


13
The quantities ( are defined above
14
The change of vibrational frequencies in the excited state due to the change of bonding.
15
This is a fairly complicated effect known as Duschinsky rotation. Is arises from the fact that the force field
of the molecule is different for each electronic state. Thus, the shapes of normal modes also change from state
to state which leads to additional complexity in the calculation of FC factors.
16
For a detailed recent discussion see Petrenko, T.; Neese, F. (2007) Analysis and Prediction of Absorption
Bandshapes, Fluorescence Bandshapes, Resonance Raman Intensities and Excitation Profiles using the Time
Dependent Theory of Electronic Spectroscopy. J. Chem. Phys., 127, 164319; Neese, F.; Petrenko, T.;
Ganyushin, D.; Olbrich, G. (2007) Advanced Aspects of ab initio Theoretical Spectroscopy of Open-Shell
Transition Metal Ions. Coord. Chem. Rev., 205, 288-327.
!"#$%&'&(")'* ,-./(01 23 ')4 3'#') 5$67&8"07"$9 B;

I|gure S: I||ustrat|on of the Iranck-Condon pr|nc|p|e. 1he exc|tat|on |nto e|ectron|c band |nvo|ves the coexc|tat|on of
v|brat|ona| |eve|s wh|ch resu|ts |n the v|brat|ona| progress|on of the absorpt|on. 1he v|bron|c peak of max|mum |ntens|ty
corresponds to the exc|ted-state v|brat|ona| |eve| wh|ch |s most c|ose to the |ntersect|on of the vert|ca| trans|t|on (red
||ne) w|th the exc|ted-state LS. As a resu|t the max|mum of the broadened absorpt|on spectrum occurs c|ose to the
vert|ca| trans|t|on energy. Ior the IMDnC mode| the number of |ntense peaks |n the absorpt|on progress|on corre|ates
w|th the va|ue of .

Let us consiuei in moie uetail the quantitative aspects of the vibiational stiuctuie in
optical spectia. In the haimonic appioximation the nuclei motion coiiesponuing to the
giounu anu exciteu electionic states is uesciibeu accoiuing to the Bamiltonians

H
N
(0)
anu

H
N
(I )
, iespectively:

H
N
(0)
= !
!
2
2M
i
i
3M
"
#
i
2
+
1
2
V
ij
(0)
X
i
X
j
ij
3M
"

(1S)

H
N
(I )
= !
!
2
2M
i
i
3M
"
#
i
2
+
1
2
V
ij
(I )
X
i
!X
i 0
(I )
( )
X
j
!X
j 0
(I )
( )
ij
3M
"

(14)
wheie

V
ij
(0)
{ }
anu

V
ij
(I )
{ }
aie the Bessian matiices foi the giounu anu

I -th exciteu state.

X
i
{ }
aie the Caitesian cooiuinates of the nuclei in the fiame of iefeience which oiigin
coiiesponus to the equilibiium positions of the nuclei foi the giounu electionic state.

X
i 0
(I )
{ }
aie the Caitesian uisplacements of the nuclei equlibiium positions in exciteu
state

I ielative to the giounu state.
!"#$%&'&(")'* ,-./(01 23 ')4 3'#') 5$67&8"07"$9 B<
Note, that if

H
N
(0)
anu

H
N
(I )
aie iuentical, i.e.

V
ij
(I )
=V
ij
(0)
anu

X
i 0
(I )
= 0 foi all

i ,

j , then the
giounu- anu exciteu-state vibiational Bamiltonians aie chaiacteiizeu by the common set
of vibiational eigenfunctions, so that

!
0
0 ( )
!
0
I ( )
=1, whieas all othei integials

!
0
0 ( )
!
n
I ( )
= 0. As soon as the equilibiium positions of atoms in the exciteu state aie
changeu compaieu to the giounu state (

X
i 0
(I )
! 0 ), anuoi theie is a change in the foice
constants

V
ij
(I )
!V
ij
(0)
, then

!
0
0 ( )
!
0
I ( )
<1, anu theie will be ceitain vibiational levels

!
n
I ( )

foi which

!
0
0 ( )
!
n
I ( )
! 0. This means that one woulu obseive uiffeient tiansitions
between the giounu vibiational level in the giounu state anu vaiious vibiational levels
coiiesponuing to the exciteu state. The intensity pattein of such a vibiational stiuctuie
uepenus in a iathei complicateu way on the uiffeience between

H
N
(0)
anu

H
N
(I )
.
0pon appiopiiate lineai tiansfoimation fiom Caitesian to noimal cooiuinates it is
possible to obtain uecoupleu iepiesentation of

H
N
(0)
anu

H
N
(I )
, which eigenfunctions aie
the piouucts of one-uimensional Beimitian functions of noimal cooiuinates.
Consiuei paiticulai case

V
ij
(I )
=V
ij
(0)
=V
ij
foi all

i ,

j , foi which, as can be shown, theie is
no change in vibiational fiequencies anu shapes of noimal moues between the giounu
anu exciteu states. Let us assume also that the equilibiium positions of atoms in the
exciteu state aie changeu compaieu to the giounu state (

X
i 0
(I )
! 0 ). A given vibiational
state

!
n
I ( )
is completely ueteimineu by a set

n
!
{ }
of occupation numbeis foi inuiviuual
moues with fiequencies

!
"
. In such a case


!
0
0 ( )
!
n
I ( )
2
=
(s
"
)
n
"
n
"
!
e
!s
"
"
3M!6
"

(1S)
wheie

s
!
=
(!
!
)
2
2
aie the so-calleu Buang-Rhys factois, anu

!
!
is uisplacement of the
exciteu-state oiigin ielative to the giounu-state one along uimensionless noimal
cooiuinate

! which can be ielateu to

X
i 0
(I )
{ }
as follows:
!"#$%&'&(")'* ,-./(01 23 ')4 3'#') 5$67&8"07"$9 B=


!
!
=
"
!
!
"
#
$
$
$
$
%
&
'
'
'
'
'
1/2
U
k!
X
i 0
(I )
M
k
k=1
3M
(

(16)

U
m!
{ }
is the oithogonal matiix obtaineu upon numeiical uiagonalization of the mass-
weighteu Bessian matiix.
Thus, one can obseive in a given electionic banu a manifolu of vibiational tiansitions at
eneigies


E
n
=E
0
+ n
!
!"
!
!
3M!6
"
(17)
coiiesponuing to uiffeient sets

n
!
{ }
, which have ielative intensities given by the
values of

!
0
0 ( )
!
n
I ( )
2
in eq. (1S).

E
0
is the sepaiation between the giounu- anu exciteu-
state PES minima. The veitical tiansition eneigy anu

E
0
can be ielateu in the following
way:

E
V
=E
0
+ !!
"
s
"
"
3M!6
"
(18)
In geneial, the intensity pattein can be quite complicateu if theie aie many moues
chaiacteiizeu by significant uisplacements. As one can see, foi the single-moue species,
like uiatomic molecules, the ielative intensities aie given by the values

s
n
n!
e
!s
which
iesult in a iathei simple chaiactei of vibiational piogiession. Figuie S illustiates this
case foi

!= 2.9 . Foi the one-uimensional species one can show that

n coiiesponuing
to the most intense vibiational tiansition satisfies the conuition

n !s , anu the numbei
of the most significant vibiational tiansitions is close to

2s .
!?B?B S&1.'&$ "A($-=12 "12=&21'-#. #K TF7#)%'-#. <%(=')1
The calculation of electionically exciteu states of molecules piesents a numbei of
auuitional challenges to quantum chemistiy that can not be uiscusseu in uepth in the
fiamewoik of this couise (foi some aspects of accuiate tieatments see chaptei +))#)U
:(K()(.=( 7#&)=( .#' K#&.;?, in paiticulai +))#)U :(K()(.=( 7#&)=( .#' K#&.;?). Beie
we puisue a iathei simple pictuie of the excitation piocess as involving the piomotion
of an election fiom an occupieu moleculai oibital in the giounu-state into an
unoccupieu oibital (one-election pictuie). Within this appioximation, the assignment of
!"#$%&'&(")'* ,-./(01 23 ')4 3'#') 5$67&8"07"$9 B>
an absoiption spectium consists of the ueteimination which uonoi anu acceptoi N0s
give the uominant contiibution to the obseiveu absoiption banus as exemplifieu above.
In geneial, this pictuie is oveisimplifieu since the exciteu state is usually not well
iepiesenteu in teims of a single Slatei ueteiminant anu seconuly, the oibitals of the
giounu state will not be appiopiiate foi the electionically exciteu state. Neveitheless,
the simplest ieasonable appioximation is to wiite the giounu state as a single
ueteiminant (foi example, the Baitiee-Fock ueteiminant):


!
0
= !
1
...!
i
...!
N
(
19)
Anu the exciteu states may be assumeu to be iepiesenteu as a supeiposition of singly-
exciteu ueteiminants:


!
I
= t
i
a
!
i
a
i,a
"
( 2u)
Wheie the ,exciteu ueteiminants"

!
i
a
have an occupieu N0

!
i
ieplaceu by a viitual N0

!
a
anu the quantities

t
i
a
aie the "amplituues" of the excitation. The quantity

t
i
a
( )
2
is the
"weight" of the exciteu ueteiminant

!
i
a
in the exciteu state

!
I
. The amplituues aie
ueteimineu fiom solving the so-calleu 20.9,58+4/,0.A,./&+42/,0. I,/% 1,.53&
&)2,/4/,0.1 9BJ;: eigenvalue pioblem. The eigenvalues of this matiix coiiesponu to the
(veitical) excitation eneigies at this level of appioximation anu the eigenvectois aie the
excitation amplituues.
17
Calculations in the CIS fiamewoik uo not leau to veiy accuiate
iesults but aie suitable to pioviue an initial oiientation piioi to moie accuiate
calculations anu is also feasible foi laigei molecules.
In the fiamewoik of uensity functional theoiy (BFT), one employs the so-calleu /,-&
>&*&.>&./ >&.1,/6 98.2/,0.43 /%&0+6 Q$7A7?$R in-oiuei to pieuict veitical tiansition
eneigies. TB-BFT is baseu on a uiffeient philosophy than CIS but leaus to equations that
aie faiily similai anu that can be solveu with compaiable computational effoit. The
accuiacy of TB-BFT is usually supeiioi to that pioviueu by CIS.
18

In 0RCA CIS oi TB-BFT calculations aie invokeu with the block:

17
Note that there is a different set of excitation amplitudes for each excited state.
18
However, there are many problems with that method and a number of artifacts are known that one should be
aware of before applying the method in actual calculations. Some of the relevant aspects are discussed in
Neese, F. (2006) A Critical Evaluation of DFT, including Time-Dependent DFT, Applied to Bioinorganic
Chemistry. J. Biol. Inorg. Chem., 11, 702-711
!"#$%&'&(")'* ,-./(01 23 ')4 3'#') 5$67&8"07"$9 B?

Foi BF iefeience wavefunction (RBF oi 0BF) the piogiam automatically chooses CIS
calculations anu foi BFT mouel (RKS oi 0KS) TB-BFT. Below is a summaiy of vaiiables
that can be assigneu within the block:

1ab|e 2: Var|ab|es for CIS or 1D-DI1 ca|cu|at|ons w|th the CkCA program.
41)-1F2( N(7=)-%'-#.
NRoots=N
Calculate the fiist N exciteu states
Triplets
Paiametei is only valiu foi closeu shell iefeiences. If chosen as true the piogiam
will also ueteimine the tiiplet excitation eneigies in auuition to the singlets
Ewin e
0
, e
1

Slects the N0s within the oibital eneigy iange |eu, e1j (Eh) to be incluueu in the
coiielation tieatment
MaxDim
The maximum uimension of the expansion space in the Baviuson pioceuuie. If
NaxBim ) S-1u times NRoots the calculations will show favoiable conveigence
but also incieaseu uisk space uemanus
Etol
uives the iequiieu conveigence of the eneigies of the exciteu states (in Eh)
RTol
uives the iequiieu conveigence on the noim of the iesiuual vectois.
TDA
Paiametei is valiu foi TB-BFT tieatment. If chosen as true the so-calleu Tamm-
Bancoff appioximation (TBA) is invokeu. Foi hybiiu functionals the choice
TDA=true is iequiieu anu will be enfoiceu by the piogiam.
Mode=riints
Invokes the methou that allows to use RI-integials tiansfoimeu to the N0 basis to
geneiate the CI matiix. It shows speeuups on the oiuei of 1u oi moie. An
auxiliaiy basis set neeus to be assigneu if this option is useu.

Beie is the key pait of the 0RCA output fiom a TB-BFT oi CIS calculation:

In this pait of the output the iesults on each state aie summaiizeu, incluuing the
excitation eneigy (in atomic units, ev anu cm
-1
), anu the laigest amplituues (squaieu) in
the CI expansion. Foi example, the 1
st
exciteu state is mainly piesenteu by one leauing
configuiation (with the weight of u.988777) in which the spin-up oibital 78 (the "uonoi
N0") in the iefeience ueteiminant is ieplaceu with the viitual oibital 8u (the "acceptoi
%cis end

# or equivalently

%tddft end
------------------------------------
TD-DFT/TDA EXCITED STATES (SINGLETS)
------------------------------------

the weight of the individual excitations are printed if larger than 0.01

STATE 1: E= 0.095176 au 2.590 eV 20888.6 cm**-1
78a -> 80a : 0.988777 (c= 0.99437248)

STATE 2: E= 0.108238 au 2.945 eV 23755.5 cm**-1
79a -> 80a : 0.945608 (c= -0.97242400)
79a -> 83a : 0.010346 (c= 0.10171342)
!"#$%&'&(")'* ,-./(01 23 ')4 3'#') 5$67&8"07"$9 B@
N0"); the symbol "a" in the output next to the oibital numbei means that this is a spin-
up oibital; alteinatively, "b" coiiesponus to spin-uown oibitals.
Tiansition eneigies anu oscillatoi stiengths foi the calculateu exciteu states aie given in
the following pait of the output:

The column fosc shows calculateu oscillatoi stiengths. TX, TY, TZ aie the components
of electionic tiansition uipole moment (in atomic unit), T2 is the squaie of tiansition
moment.
The output of iotatoiy stiengths foi the calculateu exciteu states has similai stiuctuie:

The column R shows calculateu iotatoiy stiengths. MX, MY, MZ aie the components of
electionic tiansition uipole moment (in atomic unit).
If you want to obtain a plot of the absoiption spectium then call the small utility
piogiam orca_mapspc:

The piogiam will piouuce outputfile.abs.dat file containing absoiption
spectium that can be plotteu with stanuaiu giaphics piogiams. 0ptions aie explaineu
heie:



-x0value
Stait of the x-axis foi the plot
-x1value
Enu of the x-axis foi the plot
-wvalue
Full-wiuth at half-maximum height in cm
-1
foi each tiansition
-----------------------------------------------------------------------------
ABSORPTION SPECTRUM
------------------------------------------------------------------------------
State Energy Wavelength fosc T2 TX TY TZ
(cm-1) (nm) (au**2) (au) (au) (au)
------------------------------------------------------------------------------
1 20888.6 478.7 0.094387411 1.48758 0.08858 -1.21644 -0.00006
2 23755.5 421.0 0.167847587 2.32609 -0.00002 -0.00013 -1.52515
3 32083.8 311.7 0.295677742 3.03395 0.13992 1.73619 0.00009
-----------------------------------------------------------------------------
CD SPECTRUM
------------------------------------------------------------------------------
State Energy Wavelength R MX MY MZ
(cm-1) (nm) (1e40*cgs) (au) (au) (au)
------------------------------------------------------------------------------
1 20888.6 478.7 3.659617854 0.32713 0.01744 -0.00002
2 23755.5 421.0 -166.793655155 0.96929 -0.50766 0.23200
3 32083.8 311.7 329.282848783 0.42056 0.36840 -0.12245
orca_mapspc outputfile abs x015000 x135000 w200 n2000
!"#$%&'&(")'* ,-./(01 23 ')4 3'#') 5$67&8"07"$9 BA
-nvalue
Numbei of points to be useu

Thus, in the above example the absoiption spectium will be piouuceu foi 2uuu
equiuistant points in the iange 1Suuu-SSuuu cm
-1
using full-wiuth at half-maximum
height equal to 2uu cm
-1
foi each tiansition.
Likewise, CB plot can be obtaineu by calling orca_mapspc with anothei option:

The piogiam will piouuce outputfile.cd.dat file containing CB spectium.
!?B?V 9: 1.; :1$1. 7%(=')#7=#%>
!"#":"! K0+-43 L0>&1 4.> F,G+4/,0.43 ?+&H8&.2,&1
Infiaieu (IR) anu Raman spectioscopies aie mutually complementaiy paits of moleculai
vibiational spectioscopy. Theii moleculai physics is essentially the same since both aie
conceineu with the obseivation of the excitation of moleculai vibiational eneigy states
associateu with the electionic giounu-state PES. In IR spectioscopy, vibiational
excitations occui upon the absoiption of electiomagnetic iauiation. In Raman
measuiements the excitation is a consequence of inelastic light scatteiing by molecule.
0pon the assumption that the PES is quauiatic in atomic uisplacements (haimonic
mouel) the vibiational states of an ;-atom molecule aie uesciibeu as a supeiposition of
S;-6 (S;-S foi lineai molecules) inuepenuent haimonic oscillatois which uesciibe the
collective haimonic vibiational motion of the nuclei about theii equilibiium
configuiation. The shapes of uiffeient vibiations aie chaiacteiizeu by uiffeient patteins
of the joint nucleai uisplacements anu aie calleu .#)$12 $#;(7 Q=##);-.1'(7R.
19
They
tiansfoim unuei the iiieuucible iepiesentations of the moleculai symmetiy gioup anu
may theiefoie be classifieu by theii symmetiy. The textbook example of the B20
molecule is shown in Figuie 6.
2u


19
Their construction will not be pursued in this course.
20
Still the most popular book that describes the calculation and use of normal coordinates from force fields in
detail is classic text: Wilson, E.B.; Decius, J.C.; Cross, P.C. Molecular Vibrations The Theory of Infrared and
Raman Spectra, Dover, New York, 1980; the original text is from 1955.
orca_mapspc outputfile cd x015000 x135000 w200 n2000
!"#$%&'&(")'* ,-./(01 23 ')4 3'#') 5$67&8"07"$9 :C

I|gure 6: 1he norma| coord|nates of the n
2
C mo|ecu|e together w|th |ts Ik and kaman spectra on natura| abundance as
we|| as |sotop|ca||y |abe|ed forms of n
2
C.
A quantum mechanical tieatment pioviues the exact vibiational eneigies foi the
haimonic oscillatoi mouel:

E =!!
1
(n
1
+
1
2
)+!!
2
(n
2
+
1
2
)+!!
3
(n
3
+
1
2
)+ (
21)
wheie

n
i
= 0, 1, 2, 3... aie the vibiational quantum numbeis anu

!
i
aie haimonic
vibiational fiequencies coiiesponuing to the 7-th noimal moue. Foi a puiely haimonic
oscillatoi the solution of the wavefunctions is shown in Figuie 7. (*=+2,).

I|gure 7: L|genfunct|ons and e|genenerg|es of the harmon|c osc|||ator.
The vibiational fiequencies of the noimal moues ieflect the K#)=(HK-(2; oi the molecule.
It is a measuie of the shape of the PES of the electionic state unuei investigation (usually
the electionic giounu state) which, in tuin, is uepenus on the stiengths of the bonus
!"#$%&'&(")'* ,-./(01 23 ')4 3'#') 5$67&8"07"$9 :B
between the uiffeient nuclei. Foi a uiatomic molecule, the K#)=( =#.7'1.' 4 is simply the
seconu ueiivative of the electionic eneigy at the equilibiium uistance:


k =
!
2
E
I ( )
!R
2
R=R
(
22)
Fiom which the vibiational fiequency is ieauily calculateu as:
21



! =
1
2"c
k
m
(
2S)
Wheie the ieuuceu mass % is uefineu in Figuie 8 below.

I|gure 8: V|brat|ons of a d|atom|c mo|ecu|e.
Foi a geneial polyatomic molecule, the uefinition of the foice constant must be
geneializeu. It is ieplaceu by the O(77-1. $1')-, alieauy useu extensively in the
pievious computei expeiiments. Its uefinition is:


H
AB
=
!
2
E
I ( )
!X
A
!X
B
X
A
=X
B
=...X
(
24)
(XA, XB,. aie Caitesian cooiuinates of atoms A,B,.) Essentially, uiagonalization of the
mass weighteu Bessian matiix (

!
H
AB
=H
AB
m
A
m
B
( )
"1/2
) yielus the noimal moues anu
haimonic vibiational fiequencies of the system.

21
For correct units and conversion factors see chapter Error! Reference source not found.
!"#$%&'&(")'* ,-./(01 23 ')4 3'#') 5$67&8"07"$9 ::
!"#":"# ;&3&2/,0. <83&1
The impoitant uiffeience between IR anu Raman spectioscopies is that foi non-zeio IR
intensity theie must be a change of uipole moment along a given noimal moue. Foi
uiatomic molecules, this means that they must have a peimanent uipole moment in
oiuei to be IR active. Foi nonzeio Raman intensities theie must be a change in the
polaiizability uuiing the vibiation.
Taking into account only lineai teims in vaiiations of uipole moment (foi IR) anu
polaiizability (foi Raman) uuiing the vibiation leaus to the vibiational selection iule foi
haimonic case. It states that only excitations with

!n =1 in only one single moue aie
alloweu upon the vibiational tiansition. Foi such a case, IR anu Raman spectia consist
only of funuamental tiansitions at the fiequencies which coinciue with the vibiational
haimonic fiequencies of the molecule. The use of gioup theoiy anu symmetiy
aiguments can be of gieat assistance in ueteimining of which vibiations aie IR oi
Raman active anu which aie not. Chaiactei tables foi the vaiious symmetiy gioups can
be useu to pieuict how many of the SN-6 vibiations aie IR active anu how many aie
Raman active. In paiticulai, if the symmetiy point gioup possesses a centei of inveision,
theie is a mutual exclusion iule which states that vibiations alloweu in the Raman
spectium aie foibiuuen in IR, anu vice veisa. The symmetiy of a molecule may also
uictate that ceitain banus aie foibiuuen in both the IR anu Raman spectia, in which case
even the combination of the two spectia will not pioviue the full infoimation about the
S<-6 noimal fiequencies.
!"#":": M.%4+-0.,2,/,&1
A moie uetaileu tieatment of the vibiational spectia of molecules can be maue if
anhaimonicity is incluueu into consiueiation. In this case the quauiatic mouel foi PES
function is extenueu by cubic anu highei-powei teims.
22
The occuiance of
anhaimonicities has seveial impoitant consequences foi vibiational spectioscopy.
1. Fiist, the eneigy levels aie no longei equally spaceu.
2. The fiist tiansition

n '' = 0 !n ' =1 (so-calleu K&.;1$(.'12 tiansition) occuis at a
slightly lowei fiequency than in the haimonic case.
S. The vibiational selection iule

!n =1 bieaks uown anu leaus to the obseivation of
oveitone vibiations in the expeiimental spectia. Because the eneigy levels aie no

22
Such anharmonicities will be studied in chapter Error! Reference source not found. for diatomic
molecules.
!"#$%&'&(")'* ,-./(01 23 ')4 3'#') 5$67&8"07"$9 :;
longei equiuistant, the positions of the oveitones aie not given by integei multiples
of the funuamental fiequency

n '' = 0 !n ' =1.
4. In auuition to oveitones, *,%87!&+7,! 8&!/- become weakly alloweu in which two
uiffeient vibiational moues aie simultaneously exciteu.

I|gure 9: Descr|pt|on of overtone, comb|nat|on and "hot" bands |n Ik and kaman spectra.
!"#":"= J10/0*& ;%,9/1
Since the vibiational eneigies uepenu on the masses of the vibiating atoms it is possible
to isotopically label the compounus of inteiest in oiuei to aiiive at an expeiimentally
substantiateu assignment of the expeiimental spectia of in oiuei to assist the fitting of
the foice fielus of molecules. In the case of a uiatomic molecule, the isotiope shift is
paiticulaily tianspaient since the foim of the ieuuceu mass is simply mAmB(mA+mB)
wheie mA anu mB aie the masses of the two vibiating atoms (see)

I|gure 10: 1he reduced mass and |sotope sh|fts |n v|brat|ona| spectra of d|atom|c mo|ecu|es.

!"#$%&'&(")'* ,-./(01 23 ')4 3'#') 5$67&8"07"$9 :<
!?B?L S&1.'&$ "A($-=12 "12=&21'-#. #K 9: 1.; :1$1. <%(=')1
Within the haimonic appioximation IR anu Raman vibiational spectia aie calculateu in
the couise of fiequency calculations. Since haimonic vibiational fiequencies aie
ueteimineu by the value of the Bessian matiix at the giounu-state equilibiium
geometiy, it is necessaiy that fiequencies aie calculateu foi the geometiical stiuctuie
optimizeu at the same level of theoiy as the fiequency job. 0RCA fiequency calculation is
iequesteu by NumFreq keywoiu which can be combineu with keywoiu Opt in oiuei to
peifoim geometiy optimization piioi to the fiequency iun. The %freq block contains
some algoiithm-specific infoimation:

IR spectial intensities aie calculateu automatically in fiequency iuns. Beie is the pait of
the output of a fiequency calculation containing infoimation on IR intensities:
The Mode inuicates the numbei of the vibiational moues, then the vibiational fiequency
follows. The value T**2 is the squaie of the change of the uipole moment along a given
vibiational moue in KNmole. This numbei is uiiectly piopoitional to the intensity of a
given funuamental in an IR spectium.
0se orca_mapspc piogiam to plot IR spectium:

The piouuceu outputfile.ir.dat file will contain the IR spectium. In oiuei to
pieuict the Raman spectium of a compounu one has to know the ueiivatives of the
polaiizability with iespect to the noimal moues. Thus, the Raman spectium will be
automatically calculateu if a fiequency iun is combineu with a polaiizability calculation
which is iequesteu with the block:
%freq CentralDiff true # use central-differences
# (default is false)
Increment 0.02 # increment in bohr for the
# differentiation (default 0.005)
end
-----------
IR SPECTRUM
-----------

Mode freq (cm**-1) T**2 TX TY TZ
-------------------------------------------------------------------
6: 1278.77 6.157280 ( -2.481387 -0.000010 -0.000287)
7: 1395.78 29.682711 ( -0.000003 -5.448182 -0.004815)
8: 1765.08 4.180497 ( 0.000537 -0.022003 2.044508)
9: 2100.53 8.550050 ( 0.000080 0.011990 2.924022)
10: 3498.72 1.843422 ( 0.001027 -0.178764 -1.345907)
11: 3646.23 19.778426 ( 0.000035 4.446922 -0.057577)

orca_mapspc outputfile ir w20
!"#$%&'&(")'* ,-./(01 23 ')4 3'#') 5$67&8"07"$9 :=

The output consists of the Raman activity (in A
4
AN0) anu the Raman uepolaiization
iatios:


As with IR spectia you can get a plot of the Raman spectium using:

The piouuceu outputfile.raman.dat file will contain the Raman spectium.
!?V N(7=)-%'-#. #K 'A( +,%()-$(.'
!?V?! "12=&21'-#. #K 3456-7 7%(=')1?
WT:@ !0 Calculate the absoiption spectia of the piotonateu anu unpiotonateu foims of
the uye methyl oiange (Figuie 11). Since the two foims show uistinct absoiption
spectia, such uyes can be useu as pB inuicatois. The piotonateu foim (pB<S.1) is
chaiacteiizeu by intense absoiption in the blue-gieen spectial iange (4Su-SSu nm),
while the absoiption of the uepiotonateu foim (pB>4.4) mainly occuis in the violet-blue
iange (4uu-47u nm) (Figuie 11).
2S
Consequently, upon a change of the pB fiom S.1 to
4.4, methyl oiange changes its coloi fiom ieu to yellow. In this expeiiment you shoulu
tiy to unueistanu this change.
We aie inteiesteu in the calculation of the most intense electionic absoiption banu of
both, the piotonateu anu the unpiotonateu foim of methyl oiange. Below we specify the
input files which contain geometiies.
24
TB-BFT calculations foi the 1u lowest exciteu
states will be caiiieu out. The C0SN0 appioach is applieu in oiuei to mouel the solvent

23
Nero, J.D.; Araujo, R.E.; Gomes, A.S.L.; Melo, C.P.; (2005) J. Chem. Phys., 122, 104506.
24
Optimized with BP86/SV(P)
%elprop CalcPolar true
end

--------------
RAMAN SPECTRUM
--------------

Mode freq (cm**-1) Activity Depolarization
--------------------------------------------------
6: 1278.77 0.007349 0.749649
7: 1395.78 3.020010 0.749997
8: 1765.08 16.366586 0.708084
9: 2100.53 6.696490 0.075444
10: 3498.72 38.650431 0.186962
11: 3646.23 24.528483 0.748312

orca_mapspc outputfile raman w20
!"#$%&'&(")'* ,-./(01 23 ')4 3'#') 5$67&8"07"$9 :>
effect on the calculateu tiansition eneigies of the species in aqueous solution (keywoiu
cosmo(water)in the input line). We use the Sv(P)+ basis set.
2S




I|gure 11: C|s |somers of the a|ka||ne and monoprotonated azon|um forms of methy| orange wh|ch ex|st |n a|ka||ne and
ac|d|c cond|t|ons, respect|ve|y. Lxper|menta| UV]v|s spectra of (a) aqueous and (b) acetone so|ut|ons of methy| orange
for d|fferent va|ues of the pn.


25
This basis set, although being small, includes diffuse functions since they are important for the quality of
excited-state calculations.
!"#$%&'&(")'* ,-./(01 23 ')4 3'#') 5$67&8"07"$9 :?

#
# Calculate absorption spectrum of the cis isomer of the
# monoprotonated azonium form of methyl orange molecule
#

! RKS BP86 RI SV(P)+ TightScf cosmo(water)

%basis Aux Auto end

%tddft
mode riints
NRoots 10
MaxDim 200
triplets false
end

* int 0 1
S 0 0 0 0.000000 0.000 0.000
O 1 0 0 1.503294 0.000 0.000
O 1 2 0 1.505496 113.903 0.000
O 1 2 3 1.504846 113.963 132.114
C 1 2 3 1.821147 105.823 246.180
C 5 1 2 1.412488 118.923 184.915
H 6 5 1 1.101906 119.884 1.391
C 6 5 1 1.396656 120.278 181.201
H 8 6 5 1.099690 121.170 179.947
C 8 6 5 1.415430 119.104 359.943
C 5 1 2 1.405438 120.673 5.790
H 11 5 1 1.101105 119.344 358.753
C 11 5 1 1.401946 119.910 178.849
H 13 11 5 1.102862 120.413 180.017
N 10 8 6 1.407048 121.294 179.582
N 15 10 8 1.292068 122.718 359.407
C 16 15 10 1.355081 121.021 180.663
C 17 16 15 1.435712 115.336 179.613
H 18 17 16 1.101331 117.832 0.440
C 18 17 16 1.379608 121.689 180.593
H 20 18 17 1.098042 118.873 179.922
C 20 18 17 1.441237 120.588 0.036
C 17 16 15 1.438195 126.765 359.889
H 23 17 16 1.102101 121.369 359.401
C 23 17 16 1.379013 120.789 179.375
H 25 23 17 1.098225 118.466 180.009
N 22 20 18 1.355001 121.367 179.530
C 27 22 20 1.466602 120.443 359.964
H 28 27 22 1.112145 110.957 60.750
H 28 27 22 1.105488 109.004 180.193
H 28 27 22 1.112207 110.954 299.654
C 27 22 20 1.467211 120.863 180.183
H 32 27 22 1.111950 111.045 299.134
H 32 27 22 1.105431 108.919 179.800
H 32 27 22 1.111988 111.009 60.471
H 15 10 8 1.037594 115.838 179.885
*
!"#$%&'&(")'* ,-./(01 23 ')4 3'#') 5$67&8"07"$9 :@

#
# Calculate absorption spectrum of the cis isomer of the
# alkaline form of methyl orange molecule
#

! RKS BP86 RI SV(P)+ TightScf cosmo(water)

%basis Aux Auto end

%tddft
mode riints
NRoots 10
MaxDim 200
triplets false
end


* int -1 1
S 0 0 0 0.000000 0.000 0.000
O 1 0 0 1.505131 0.000 0.000
O 1 2 0 1.506757 113.600 0.000
O 1 2 3 1.506150 113.681 131.250
C 1 2 3 1.818920 106.015 245.700
C 5 1 2 1.413708 118.996 185.848
H 6 5 1 1.102898 119.621 1.627
C 6 5 1 1.396697 120.074 181.327
H 8 6 5 1.100787 121.258 179.965
C 8 6 5 1.422751 120.253 359.920
C 5 1 2 1.405535 120.698 6.867
H 11 5 1 1.101648 119.146 358.587
C 11 5 1 1.403465 119.673 178.764
H 13 11 5 1.102720 121.111 179.947
N 10 8 6 1.410630 124.803 179.669
N 15 10 8 1.282691 114.919 359.230
C 16 15 10 1.393811 116.204 180.367
C 17 16 15 1.420530 116.764 179.724
H 18 17 16 1.102756 118.044 0.310
C 18 17 16 1.392566 121.688 180.427
H 20 18 17 1.098954 118.761 179.958
C 20 18 17 1.434004 120.756 0.043
C 17 16 15 1.424999 125.381 0.000
H 23 17 16 1.101255 118.390 359.646
C 23 17 16 1.389114 121.131 179.553
H 25 23 17 1.099517 118.637 179.995
N 22 20 18 1.371544 121.464 179.666
C 27 22 20 1.460234 120.164 359.930
H 28 27 22 1.114577 111.584 60.709
H 28 27 22 1.106833 109.151 180.161
H 28 27 22 1.114654 111.583 299.634
C 27 22 20 1.460612 120.462 180.172
H 32 27 22 1.114413 111.662 299.198
H 32 27 22 1.106774 109.075 179.828
H 32 27 22 1.114474 111.629 60.462
*
!"#$%&'&(")'* ,-./(01 23 ')4 3'#') 5$67&8"07"$9 :A

Fiom the output, ueteimine the most intense tiansitions, theii excitation
eneigies anu theii oscillatoi stiengths. Aie the vaiiations of tiansition eneigies
consistent with expeiimentally obseiveu spectial changes between two foims of
methyl oiange.
Analyze the electionic stiuctuie of the two foims. Beteimine the natuie of the
most intense tiansitions by inspecting the shapes of uonoi anu acceptoi N0s
with a visualization piogiam. Bow uo these oibitals change upon going fiom
unpiotonateu to piotonateu species.
0se the orca_mapspc piogiam to plot absoiption spectia in the visible spectial
iange anu compaie them with the expeiimental spectia.
WT:@ B0 Calculate the vibiational stiuctuie of the absoiption banu anu iesonance
Raman spectia coiiesponuing to the electionic tiansition 1
1
Ag &1
1
Bu of tians-1,S,S-
hexatiien. Assuming the IBNB0 mouel, the calculation of vibionic stiuctuie in
absoiption spectia
26
foi uipole-alloweu tiansitions involves two stages. Fiist one
shoulu calculate the tiansition eneigy, tiansition uipole moment anu oiigin
uisplacement of the exciteu state ielative to the giounu state along totally symmetiic
noimal moues. 0n the seconu stage the calculateu paiameteis aie employeu in oiuei
to simulate the absoiption spectium in a usei-specifieu spectial iange. Within the
haimonic appioximation, the oiigin uisplacements along uiffeient noimal moues
may be appioximateu by means of exciteu-state eneigy-giauient calculations. This
type of job is specifieu below in the 0RCA input. We have useu the geometiy of
hexatiiene optimizeu at the RBFSv(P) level. The piogiam employs the Bessian
matiix obtaineu fiom a coiiesponuing fiequency calculation since it pioviues
fiequencies anu noimal moues which aie useu in the tiansfoimation of the eneigy
giauient fiom Caitesian to noimal cooiuinates. Thus, the name of the Bessian file is
specifieu in the %rr block via the keywoiu HessName.



26
as well as resonance Raman spectra; however, the resonance Raman technique will not be covered here.
!"#$%&'&(")'* ,-./(01 23 ')4 3'#') 5$67&8"07"$9 ;C

At the enu of the 0RCA iun you get the file hexatriene-uv.asa.inp which pioviues
the input infoimation foi spectial simulation. The simulation pait is peifoimeu in the
fiamewoik of Bellei time-uepenuent theoiy implementeu in stanu-alone piogiam
orca_asa.
27
The basic stiuctuie of the file is shown below. In the input you will neeu to
mouify the paiameteis conceining vaiious uetails of the simulation like spectial iange
anu numbei of points foi absoiption. The input file foi spectial simulation also contains

27
The theory is explained in Petrenko, T.; Neese, F. (2007) Analysis and Prediction of Absorption Bandshapes,
Fluorescence Bandshapes, Resonance Raman Intensities and Excitation Profiles using the Time Dependent
Theory of Electronic Spectroscopy. J. Chem. Phys., 127, 164319; Neese, F.; Petrenko, T.; Ganyushin, D.;
Olbrich, G. (2007) Advanced Aspects of ab initio Theoretical Spectroscopy of Open-Shell Transition Metal Ions.
Coord. Chem. Rev., 205, 288-327
# hexatriene-uv.inp
#
# CIS Normal Mode Gradient Calculation
#
! RHF TightSCF SV(P) Grid4 NoFinalGrid NMGrad

%cis
NRoots 1
EWin -10000, 10000
MaxDim 200
ETol 1e-7
RTol 1e-7
triplets false
end

%rr
HessName= "hexatriene.hess"
states 1 # perform energy-gradient calculation for the 1
st

#excited state
Tdnc 0.005 # threshold for dimensionless displacement to be
# included in the input file for spectra simulations
# generated at the end of the program run

ASAInput true # generate the input file for spectral simulations

end

* xyz 0 1
C -0.007965 0.666889 -0.000000
H -0.961692 1.187002 -0.000000
C 1.194639 1.503680 0.000000
H 2.146084 0.980277 0.000000
C 1.184814 2.831999 -0.000000
H 0.257404 3.396037 -0.000000
H 2.105024 3.404491 0.000000
C 0.007965 -0.666889 -0.000000
H 0.961692 -1.187002 -0.000000
C -1.194639 -1.503680 0.000000
H -2.146084 -0.980277 0.000000
C -1.184814 -2.831999 -0.000000
H -0.257404 -3.396037 -0.000000
H -2.105024 -3.404491 0.000000
*
!"#$%&'&(")'* ,-./(01 23 ')4 3'#') 5$67&8"07"$9 ;B
the following blocks specifying the paiamteies foi the INBB0 mouel which weie
calculateu upon 0RCA iun:
%el_states block specifies infoimation about each electionic state incluuing
auiabatic minima tiansition eneigy, electionic tiansition uipole moment
components, homogeneous linewiuth paiametei (Gamma), stanuaiu ueviation of
tiansition eneigy (Sigma, also calleu inhomogeneous linewiuth paiametei).
%vib_freq_gs block contains giounu-state vibiational fiequencies of
vibionically active moues.
%sdnc block specifies uimensionless noimal cooiuinate uisplacements foi
vibionically active moues.
!"#$%&'&(")'* ,-./(01 23 ')4 3'#') 5$67&8"07"$9 ;:


#
# hexatriene-uv.asa.inp
#

%sim
model IMDHO
method Heller

# spectral range for simulation of absorption:
AbsRange 40000.0, 55000.0

# number of points in the simulated absorption spectrum
NAbsPoints 5000

end

#---------------------------------------------------------------------------
# Transition Gamma Sigma Transition Dipole Moment (atomic unit)
# Energy (cm**-1) (cm**-1) (cm**-1) Mx My Mz
#---------------------------------------------------------------------------
$el_states
1
1 43422.32 50.00 0.00 -0.8533 -3.3690 -0.0000


$vib_freq_gs
13
1 373.151457
2 468.331475
3 1008.146916
4 1301.212433
5 1414.106060
6 1432.662207
7 1542.963264
8 1796.175363
9 1899.633103
10 3309.402656
11 3315.060790
12 3324.587826
13 3397.380154

$sdnc
13 1
1
1 -0.689568
2 -0.121420
3 0.332391
4 -0.998839
5 0.452707
6 0.186902
7 0.210313
8 -0.007187
9 -1.782913
10 0.034978
11 0.069401
12 0.031373
13 0.007086
!"#$%&'&(")'* ,-./(01 23 ')4 3'#') 5$67&8"07"$9 ;;
At the enu of the piogiam iun you will get the file hexatriene-uv.abs.dat
containing the absoption spectium.
Now:
Plot the spectium. Beteimine the position of the u-u vibionic peak in the
absoiption. Locate the vibionic peak with the maximum intensity anu compaie it
with the calculateu veitical tiansition eneigy. Explain the uiffeience.
Iuentify the most impoitant oveitone anu combination tiansitions in the
absoiption banu. Bow uo theii intensities coiielate with the values of
uimensionless noimal cooiuinate uisplacements given in the input.
WT:@ V0 Calculate CB spectium of the (N)-heptahelicene, Figuie 12).
28
Expeimental
tiansition eneigies anu intensities of the lowest eneigy tiansitions aie summeiizeu in
Table S.


I|gure 12: Structure of (M)-pentahe||cene and |ts exper|menta| CD spectrum.

1ab|e 3: Lxper|menta| resu|ts for the |owest exc|tat|ons of (M)-pentahe||cene |n ethano| so|ut|on.
State

!E (nm)

f

R (1u
-4u
cgs)
1 S92 u.uu2 u.1
2 S28

u.11S -1Su
S Su6 u.4uu -4uu


28
Brown, A.; Kemp, C.M.; Mason, S.F.; (1971) J. Chem. Soc. A, 751.
!"#$%&'&(")'* ,-./(01 23 ')4 3'#') 5$67&8"07"$9 ;<
Below we specify the input file which contains geometiy optimizeu at the BP86Sv(P).
TB-BFT calculations foi the 1u lowest exciteu states will be caiiieu out. The C0SN0
appioach is applieu in oiuei to mouel the solvent effect on the calculateu tiansition
eneigies anu intensities.
#
# Calculate CD spectrum of (M)-pentahelicene
#

! RKS BP86 RI SV(P)+ cosmo(ethanol)

%basis aux auto end

%tddft
mode riints
NRoots 10
MaxDim 300
triplets false
end

* xyz 0 1
C -0.032098 0.727529 0.865728
H 0.368360 -1.199356 4.290991
C 0.032098 -0.727529 0.865728
C 0.292271 -1.387042 2.114305
C -0.292271 1.387042 2.114306
C -0.954485 -1.133225 -1.443248
C -0.191948 0.661637 3.344271
C -0.616376 2.787102 2.138058
C 0.191948 -0.661637 3.344271
H -0.368360 1.199356 4.290991
C -0.242892 -1.583277 -0.290736
C 0.616376 -2.787102 2.138058
C -0.589489 3.546253 0.992284
H -0.890736 3.240068 3.105649
C -0.095388 2.985042 -0.233202
H -0.868017 4.613230 1.014928
C 0.242892 1.583277 -0.290736
C 0.147631 3.819306 -1.363589
C -0.147631 -3.819306 -1.363589
C 0.954486 1.133225 -1.443248
C 0.589489 -3.546253 0.992284
H 0.890735 -3.240068 3.105649
C 0.095388 -2.985042 -0.233202
H 0.868017 -4.613230 1.014928
C 0.784716 3.327293 -2.497196
H -0.149295 4.880184 -1.305305
C 1.221968 1.978849 -2.516823
H 0.982510 3.987823 -3.357927
C -1.221968 -1.978849 -2.516823
H 1.787046 1.595442 -3.382869
H 0.149294 -4.880184 -1.305305
C -0.784716 -3.327293 -2.497196
H -0.982510 -3.987823 -3.357927
H -1.787046 -1.595442 -3.382869
H -1.326263 -0.099422 -1.475319
H 1.326263 0.099422 -1.475319
*
!"#$%&'&(")'* ,-./(01 23 ')4 3'#') 5$67&8"07"$9 ;=
Now:
Fiom the output, ueteimine the most intense tiansitions, theii excitation
eneigies, oscillatoi stiengths, anu iotatoiy stiengths. Peifoim the assignement of
the expeiimentally obseiveu optical tiansitions.
29

Beteimine the natuie of the most intense tiansitions by inspecting the shapes of
uonoi anu acceptoi N0s with a visualization piogiam.
0se the orca_mapspc piogiam to plot CB spectium in appiopiiate spectial
iange anu compaie it with the expeiimental spectium.

WT:@ L0 Calculate the absoiption anu CB spectia coiiesponuing to the lowest eneigy
tiansition in the 1,7,7-tiimethyl-bicyclo|2.2.1jheptan-2-one (u-(+)-camphoi, Figuie 1S
).
Su



I|gure 13: Strucure of d-(+)-camphor and |ts exper|menta| UV absorpt|on (dashed ||ne) and CD (so||d ||ne) spectra |n
ethano| so|ut|on correspond|ng to the |owest energy e|ectron|c band.

We aie inteiesteu in the calculation of the low-eneigy electionic absoiption anu CB
banu of the compounu. Below we specify the input file which contains geometiy
optimizeu at the BP86Sv(P). TB-BFT calculations foi the S lowest exciteu states will be
caiiieu out. The C0SN0 appioach is applieu in oiuei to mouel the solvent effect on the
calculateu tiansition eneigies anu intensities.



29
For a discussion see also Furche, F.; Ahlrichs, R; Wachsmann, C.; Weber, E.; Sobanski, A.; Vgtle, F.;
Grimme, S.; (2000) J. Am. Chem. Soc., 122, 1717.
30
Gillard, R.D.; Mitchell, P.R.; (1969) Trans. Fraraday. Soc., 65, 2611.
!"#$%&'&(")'* ,-./(01 23 ')4 3'#') 5$67&8"07"$9 ;>

#
# Calculate the lowest energy optical transitions
# in d-(+)-camphor
#

! RKS BP86 RI SV(P)+ cosmo(ethanol)

%basis Aux auto end

%tddft
tda true
mode riints
NRoots 3
MaxDim 300
triplets false
end


* xyz 0 1
O 1.877429 6.781782 7.163138
C 1.373114 7.681449 4.918091
C 1.308771 7.598232 6.450938
C 0.405529 8.751374 6.913391
C 0.099863 9.480852 5.585535
H -0.775079 10.160694 5.637362
C 1.406490 10.155015 5.090954
H 1.881650 10.771421 5.884999
H 1.199121 10.824910 4.228371
C 2.287481 8.937404 4.662510
H 3.248107 8.870379 5.216696
H 2.533414 8.970132 3.578223
C -0.026564 8.284845 4.609006
H -0.862265 7.593915 4.861784
H -0.124454 8.594531 3.544670
C 1.813380 6.399538 4.228001
H 1.886092 6.541741 3.126493
H 1.097222 5.570740 4.426288
H 2.810451 6.077492 4.602254
H -0.517516 8.317884 7.364558
H 0.900650 9.367303 7.696537
*
!"#$%&'&(")'* ,-./(01 23 ')4 3'#') 5$67&8"07"$9 ;?
Now:
Fiom the output, ueteimine the tiansitions, which eneigy most closely matches
the expeiimental one. Beteimine the natuie of the tiansition by inspecting the
shapes of uonoi anu acceptoi N0s with a visualization piogiam.
0se the orca_mapspc piogiam to plot absoiption anu CB spectia in the spectial
iange aiounu Suu nm using appiopiiate value of the banuwiuth which ioughly
matches the expeiimental one. Compaie expeiimental anu theoietical plots.
Boes the iotatoiy stiength have the piopei sign foi the given tiansitions. What
paiametei, that can be iathei sensitive to the level of calculation, can iesult in
obseiveu uisagieement. As a hint, consiuei the the scalai piouuct of the
tiansition electiic uipole anu magnetic uipole moments in the foim

D
0!I
" M
0!I
=D
0!I
M
0!I
cos! .
!?V?B "12=&21'-#. #K 9: 1.; :1$1. 7%(=')1
WT:@ !0 0ptimize the geometiies, calculate vibiational fiequencies, IR anu Raman
intensities of the following uiatomic molecules using the BP86 functional anu the TZvP
basis set:
C0 : *exp= 217u cm
-1

BF : *exp= 41S8 cm
-1

ClF : *exp= 786 cm
-1

N2 : *exp= 2SS9 cm
-1

BCl : *exp= 2991 cm
-1

Cl2 : *exp= S6u cm
-1


Now:
Analyze the oiigin of the tienus in the calculateu IR intensities using population
analysis anu chemical intuition
Why uo the stietching vibiations of the homonucleai uiatomics uo not show any
IR intensity. Pioviue a qualitative explanation on the oiigin of IR intensity foi the
heteionucleai species.
Compaie the calculateu 5&$%,!7* fiequencies with the expeiimental 5&$%,!7*
fiequencies. Bow ieliable aie the BFT iesults.
S1


31
In general, the calculations always produce harmonic force constants and therefore also harmonic
frequencies. The underlying assumption is that the potential energy surfaces behave exactly quadratically. In
reality, however, the potentials are anharmonic and this leads to important alternations in the spacing of the
vibrational levels. Some of these aspects will be studied for diatomic molecules in section Error! Reference
source not found. on page 166. However, experimental harmonic frequencies are only known for very small
molecules and anharmonic frequencies are difficult to calculate. In practice, this limits the accuracy of the
!"#$%&'&(")'* ,-./(01 23 ')4 3'#') 5$67&8"07"$9 ;@

WT:@ B0 0ptimize the geometiy, calculate vibiational fiequencies, IR anu Raman
intensities of the benzene molecule using the BP86 functional anu the TZvP basis set.
Expeiimental vibiational fiequencies of the benzene aie known fiom IR anu Raman
measuiements:
IR : 148S cm
-1

Raman : 6uS.u, 991.6, 1178.u, 1S9S.u cm
-1


Beie is the input file foi 0RCA calculation:


Now:
Assign expeiimental vibiational fiequencies. Beteimine the chaiactei of IR anu
Raman active vibiations using the g0penNol piogiam foi visualization.
Plot the expeiimental veisus the calculateu fiequencies.
Calculate the paiameteis of a lineai iegiession analysis. Bow ieliable aie youi
pieuictions of vibiational fiequencies. What is youi mean ueviation fiom
expeiiment, what is youi maximum ueviation.
The benzene molecule possesses a centei of inveision. Show complementaiy
natuie of Raman anu IR spectia on the basis of the calculateu IR intensities anu

comparison between theory and experiment and one usually compares calculated harmonic frequencies with
observed fundamentals (which contain anharmonic contributions).
! RKS BP86 RI TZVP TZV/J TightOpt TightScf Grid4 NoFinalGrid NumFreq

%freq
CentralDiff true
Increment 0.02
end

%elprop Polar true end

# vibrational analysis of benzene molecule

* xyz 0 1
C 0.000000 -0.7000000000 1.2124355653
H 0.000000 -1.2500000000 2.1650635095
C 0.000000 -1.4000000000 0.0000000000
H 0.000000 -2.5000000000 0.0000000000
C 0.000000 -0.7000000000 -1.2124355653
H 0.000000 -1.2500000000 -2.1650635095
C 0.000000 0.7000000000 1.2124355653
H 0.000000 1.2500000000 2.1650635095
C 0.000000 1.4000000000 0.0000000000
H 0.000000 2.5000000000 0.0000000000
C 0.000000 0.7000000000 -1.2124355653
H 0.000000 1.2500000000 -2.1650635095
*
!"#$%&'&(")'* ,-./(01 23 ')4 3'#') 5$67&8"07"$9 ;A
Raman activities. Which symmetiy species aie active in IR anu which in Raman.
Which vibiations aie foibiuuen in both IR anu Raman spectia.

WT:@ V0 0ptimize the geometiies anu calculate vibiational fiequencies of the following
molecules using the BP86 functional anu the TZvP basis set:
!
:
D
:

!
:
D
<

!
:
D
>


}0B:
Biscuss the tienu in the vaiiation of fiequency of CC stietching moue between the
molecules. Bow uo the fiequencies uepenu on the bonu oiuei. Compaie the
iesults with the chaiacteiistic fiequencies known foi C-C, C=C anu C-C bonus.
0se the orca_vib piogiam to obtain estimates of the C-C stietching foice
constants. Bow uo they vaiy with bonu oiuei.
Pioviue a qualitative explanation of the obseiveu tienu on the basis of chemical
intuition.
WT:@ L0 0ptimize the geometiy, calculate vibiational fiequencies, IR anu Raman
intensities of the glycine molecule (B2N-CB2-C00B) using the BP86 functional anu the
TZvP basis set.
The input file is specifieu below:

The expeiimental IR anu Raman powuei spectia of glycine
S2
aie given in Figuie 14.

32
Kumar, S.; Rai, A.K.; Singh, V.B.; Rai, S.B.; (2005) Spectrochim. Acta Part A, 61, 2741-2746.
! RKS BP86 RI TZVP TZV/J TightOpt TightScf Grid4 NoFinalGrid NumFreq

%freq
CentralDiff true
Increment 0.02
end

%elprop Polar true end

* xyz 0 1
N 0.417502 -1.939309 0.000000
C -0.563503 -0.866622 0.000000
C 0.000000 0.555853 0.000000
H 1.029096 -1.853448 0.815576
H 1.029096 -1.853448 -0.815576
H -1.225791 -0.963395 -0.876292
H -1.225791 -0.963395 0.876292
O 1.179353 0.850856 0.000000
O -1.002263 1.487634 0.000000
H -0.564825 2.365543 0.000000
*
!"#$%&'&(")'* ,-./(01 23 ')4 3'#') 5$67&8"07"$9 <C

I|gure 14: Lxper|menta| |nfrared (a) and kaman (b) powder spectra of g|yc|ne.

The expeiimental vibiational fiequencies of weie ueteimineu as follows:
IR : Su4, S84, 6u7, 698, 89S, 1uS4, 1SS4, 141u, 1Su4, 161u,
17uS, 2128, 292u, Su84, S414 cm
-1

Raman : 497, 6u2, 697, 89S, 1uSS, 1S2S, 141u, 1Su8, 1667, 212S,
29Su, SuSu cm
-1

Now:
E*"& 7'*7%*'&64 23 ')4 3'#') 0$67&8' %0()F &G6 orca_mapspc $8"F8'#H
Assign expeiimental vibiational fiequencies. Beteimine the chaiactei of IR anu
Raman active vibiations using the g0penNol piogiam foi visualization. Finu
coiiesponuing vibiations which aie cleaily iuentifieu in both IR anu Raman
spectia.
SS
Which noimal moues have noticeable intensities only in IR oi Raman.
Plot the expeiimental veisus the calculateu fiequencies.
Calculate the paiameteis of a lineai iegiession analysis. Bow ieliable aie youi
pieuictions of vibiational fiequencies. What is youi mean ueviation fiom
expeiiment, what is youi maximum ueviation.


33
Some of the vibrations may show slightly different frequencies in IR and Raman measurements which is due
to slight variations in the wavelength calibration and the experimental conditions.
!"#$%&'&(")'* ,-./(01 23 ')4 3'#') 5$67&8"07"$9 <B