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CHIN. PHYS. LETT. Vol. 26, No. 2 (2009) 020308

Vibrational Spectroscopy of CH/CD Stretches in Propadiene: An Algebraic Approach

Joydeep Choudhury 1** , Nirmal Kumar Sarkar 2 , Srinivasa Rao Karumuri 1 , Ramendu Bhattacharjee 1

1 Department of Physics, Assam University, Silchar-788011, India 2 Department of Physics, Karimganj College, Karimganj-788710, India

(Received 18 September 2008)

Using Hamiltonian based on Lie algebraic method, the stretching vibrational modes of C 3 H 4 and C 3 D 4 molecules are calculated up to higher overtones. The model appears to describe C–H and C–D stretching modes with less number of parameters. The locality parameter confirms the highly local behaviour of the stretching modes of these molecules.

PACS: 03. 65. Fd, 31. 15. Hz

Molecular spectroscopy is an area of active inter- est and has played an important role to understand and analyse a physical system in both experimental and theoretical approaches. One of the most interest- ing areas of current research in molecular physics is the study of vibrational ground and excited states of polyatomic molecules. After the recent rapid devel- opments of sophisticated instruments, the molecular spectroscopy is currently going through an exciting time of renewed interest. Two traditional approaches have been used so far in the analysis of experimen- tal data: (i) the Dunham-like [1] expansion of energy levels in terms of rotation–vibration quantum num- bers and (ii) the solution of Schr¨odinger equation with potentials obtained either by modifying ab initio cal- culations or by more phenomenological methods. The Dunham-like expansions contain a large number of pa- rameters which can not be determined from the few available data and the model based on the solution of many body Schr¨odinger equation with interatomic potential becomes cumbersome and difficult to apply in the case of polyatomic molecules. To overcome the difficulties arises in analysing the vibrational spectra, third approach the vibron model (the algebraic mod- els) based on Lie algebra [2] was built in the second half of the 20th century. This new model seems to de- scribe the molecular spectra successfully even in com- plex situations. The algebraic models have been used extensively in a variety of fields: (i) research of spectra of atomic nuclei (interacting boson model) [3] and (ii) spectra of diatomic and triatomic molecules, [4 , 5] (iii) research of spectra of linear and quasilinear tetratomic molecules, [6] (iv) spectra of tetrahedral molecules, [7] benzene [8] and octahedral molecules, [9] (v) vibrational modes of CH bonds in n-paraffin molecules, [10] (vi) CH stretching modes of n-alkane [11] and polyethylene. [12] Iachello and Oss presented a brief review of develop- ment of algebraic techniques and its application to molecular spectroscopy [13] in last five years up to 2000. The main features and applications of these meth- ods have been described in a number of books [14 , 15] and review articles [16] in last few years. Recently we

reported the studies on vibrational spectra of HCN, OCS, [1719] HCCF, HCCD, [20] CCl 4 , SnBr 4 , [21] Ni (OEP), Ni (TPP) and Ni porphyrin [22] by an alge- braic approach. Propadiene is one of the most exten- sively studied molecules belonging to the point group D 2 . The C–H (or C–D) stretching vibrational modes of such molecules have been analysed by different au- thors, e.g. Mills and Mompean [23] and Halonen. [24] In this Letter, we initiate the use of algebraic meth- ods to generate stretching modes of C–H (C–D) bonds in propadiene molecule. The model we use is noth- ing but a one-dimensional version of the general al- gebraic model of rotation-vibration spectra of poly- atomic molecules. In this model, each bond, , is re- placed by an algebra , and the Hamiltonian describ- ing the molecule is written in terms of algebraic bond coordinates. The eigen states, eigenvalues and matrix elements of operators are then found out by algebraic manipulations which are easy to perform. We start with full algebraic Hamiltonian operator for C 3 X 4 (X=H, D) molecules. The general form of such operator can be written as

̂︀ = ̂︀ + ̂︀ + ̂︀ .

(1)

In this expression, ̂︀ describes the stretching modes ̂︀

describes the de-

generate bending modes and is constructed from the ̂︀

provides

stretch/bend interactions of several kinds based on the (2) / (3) scheme. [25] In this study, we neglect ̂︀ and ̂︀ in Eq. (1) due to lack of experimental data for bending mode. We consider the stretching Hamiltonian ̂︀ . For four one-dimensional oscillators C–X (X=H, D), we start with the spectrum generat- ing algebras (SGA), 1 (2) × 2 (2) × 3 (2) × 4 (2). Here, the two C–C oscillators (bond 5 and 6) are not considered on the basis which may definitely give the stretching vibrations as we mostly focused on C–X stretching vibrations. We then construct the local ba- sis given by

two-dimensional model (3) algebra;

and is based on (2) algebra;

** To whom correspondence should be addressed. Email: choudhuryjoy@rediffmail.com c 2009 Chinese Physical Society and IOP Publishing Ltd

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CHIN. PHYS. LETT. Vol. 26, No. 2 (2009) 020308

1 (2)

×

2 (2)

×

3 (2)

×

4 (2)

1 (2) 1

×

2 (2) 2

×

3 (2) 3

×

4 (2) 4

.

(2)

Table 1. C–H (C–D) stretching vibrational modes of C 3 H 4 and C 3 D 4 molecules. Here the observed values are taken from Ref. [23].

 

Vibrational level

Symmetry

C 3 H 4

 

C 3 D 4

calc (cm 1 )

obs (cm 1 )

calc (cm 1 )

obs (cm 1 )

1

5

2

3000.84

3015.6

2205.96

2228.9

1

1

3000.84

3006.6

2205.96

2216.6

±1

3081.25

3085.6

2310.51

2321.2

8

 

2 5 1 + 5

1

5946.81

4448.55

2

5997.96

5947.5

4409.16

4417.4

 

±1

6078.37

4513.71

 

5 +

8

2

2 1

1

5946.81

4448.55

 

±1

5997.96

5980

4409.16

 
 

1 +

8

2

±2

 

6158.78

6135.5

4618.26

4611.4

8

2

 

2

0

8

 

6025.34

 

4551.39

 

1

 

2

±2

6025.34

4551.39

8

1

3

3 5 1 + 2 5

2

8596.68

6414.12

1

8863.52

6547.2

(rms)

 

42.89 cm 1

29.53 cm 1

In this expression, we introduce the vibron num- bers (X=H,D) which are directly related to the anharmonicity of local C–H (C–D). The four stretch- ing quantum number 1 , 2 , 3 , 4 are associated with C–H (C–D) bonds (Fig. 1). The stretching Hamilto- nian for uncoupled bonds can be written as

̂︀

)

(

̂︀

̂︀

̂︀

̂︀

= ( 1 + 2 + 3 + 4 ) .

(3)

The operators ̂︀ are the Casimir invariant operators of (2) algebras, = 1 , 2 , 3, 4. Their diagonal matrix elements in the local basis 1 , 2 , 3 , 4 ⟩︀ are of the form

̂︀ = 4 ( ) ,

= 1 , 2 , 3, 4

(4)

with 1 = 2 = 3 = 4 = . Interbond cou- plings can be introduced in terms of operators associ- ated with products of (2) and (2) algebras associ- ated different, interacting bonds. We are thus led to coupled, stretching Hamiltonian operator

̂︀

(1)

=

(︀

̂︀ 12 + ̂︀ 13 + ̂︀

̂︀ 34 )︀ .

+

̂︀ 23 + 24 +

̂︀

14

(5)

The term ̂︀ leads to cross-anharmonicities between pairs of distinct local oscillators which is diagonal with matrix elements given by

⟨︀ , ; , | ̂︀ | , ; , ⟩︀

= 4[( + ) 2 ( + )( + )] .

(6)

Thus, the total Hamiltonian for coupled and uncou- pled stretching bonds is expressed by

̂︀ = ̂︀

(0)

+ ̂︀

(1)

.

(7)

The modes of four equivalent CX bond are now mixed, ̂︁

shifted and split under the action of the operator

(adjacent and opposite). The Majorana operator is used to describe local mode interactions in pairs and has both diagonal and non-diagonal matrix elements given by [9]

⟨︀ , ; ,

̂︁

, ; , ⟩︀

= + 2 ,

⟨︀ , + 1; , 1

̂︁ , ; , ⟩︀

1

= [︀ ( + 1)( )( + 1) ]︀ 2 ,

⟨︀ , 1; , + 1

̂︁ , ; , ⟩︀

1

= [︀ ( + 1)( )( + 1) ]︀ 2 , (8)

so the general algebraic Hamiltonian operator for de- scribing the C–X (X=H,D) stretching modes of propa- diene is expressed by

̂︀ =

4

∑︁

=1

̂︀ +

4

∑︁

< =1

̂︀ +

4

∑︁

< =1

̂︁ .

(9)

The strength of uncoupled and coupled bonds are reg- ulated by parameters ( ), / ( ) and = adj , respectively. The inclusion of ̂︁ in the Hamiltonian conserves the total vibrational (polyad) quantum number.

X

X

4 X 1 5 6 C C C 2 3 X
4
X
1 5
6
C C
C
2
3
X

Fig. 1. Bond numbering adopted in the C 3 X 4 (X=H, D) molecule for its algebraic representation.

In Table 1, we list the results of fits to C–H and C–D stretching fundamental and overtone modes of

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CHIN. PHYS. LETT. Vol. 26, No. 2 (2009) 020308

propadiene molecule using the model Hamiltonian (9).

From the view of group theory, the four oscillators (C– X) describe the fundamental stretching modes ( = 1)

) irreps. Here

1 represents the symmetry irreps while 1 and 2

represent antisymmetric irreps with respect to 2 per- pendicular to the principal axis, and represents two- dimensional symmetric irreps with respect to centre of inversion. There are ten stretching vibrational states

);

) and

( 1 +

man active and the remaining states are infrared ac- tive. As there are very few available data, Table 1 should be considered more a prediction of unknown states rather than a fit. It is seen from Table 2 that the parameters are different for two molecules. Here (rms) is reported as 42.89 cm 1 and 29.53 cm 1 for C 3 H 4 , C 3 D 4 molecules, respectively. We believe that more satisfactory results will be predicted if the inter- bond coupling between CH (CD) stretches at oppo- site ends of the molecules are taken into consideration in spite of their small values. Also, it is to be men- tioned here that the large number of observed data may reduce the value of (rms). The vibron num- bers for C–H and C–D bonds, ( ) were fixed to = 43 and = 61, calculated from expression {( / ) 2} with experimental potential param- eters ( = 2861 . 6 cm 1 , = 64 . 3 cm 1 for C 3 H 4 and = 2333 . 7 cm 1 , = 30 . 6 cm 1 for C 3 D 4 ) taken from Refs. [5,24].

( = 2) separates into 1 (2 5 ), 1 (2 1 ), 1 (2

given by 1 ( 1 ), 2 ( 5 ), and (

±1

8

0

8

1 (2

±2

8

); 2 ( 1 + 5 ) , 2 (2

±1

8

8

±2

); ( 5 +

±1

8

). Out of these states, 3 1 bands are Ra-

Table 2. Fitting parameters of C 3 H 4 and C 3 D 4 .

( ) ( ) / ( ) = adj

C 3 H 4

43

15 . 98

0 . 465

0.935

C 3 D 4

61

7 . 8

0 . 345

0.857

All the values are in cm 1 except which is di- mensionless. In this study we have applied the one-dimensional algebraic model to C 3 X 4 (X=H, D) molecules. The al- gebraic Hamiltonian has been used to compute their energies up to second overtones. The stretching vi- brational modes of C 3 H 4 and C 3 D 4 molecules are presented in Table 1. In the fundamental the split- ting is 80 . 41 (C–H), 104 . 55 (C–D) for C 3 H 4 and C 3 D 4 molecules. The splitting pattern deter- mines the nature of interbond interaction (our pa- rameter = adj ). The present results show that (rms) = 16 . 42 and 16.71 cm 1 for fundamentals of C 3 X 4 (X=H, D) molecules which is reasonable but becomes larger for first overtones. The theoretical predicted ( 1 + 5 ) mode of C 3 H 4 molecule (devi- ation of 50.46 cm 1 with the observed value) ques- tions the experimental accuracy by this algebraic ap- proach. The local versus normal behaviour of stretch- ing modes of C 3 X 4 can be characterized by introduc- ing the quantity, = 2 / arctan [︀ 8 adj /( + ) ]︀ . We find = 0 . 4456 for C–H bond and = 0 . 1635 for the

C–D bond, thus confirming highly local behaviour of the stretching modes of propadiene. Thus, we can say that the algebraic model Hamiltonian is successful in

predicting the energies in the complex molecular sys- tem. We would like to thank Professor S. Oss for pro- viding initial inspiration for this study. RB and SRK are grateful to DST for providing a research grant.

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