% H2 ground state from a non-relativistic Hartree Fock treatment

using STO-4G basis set and Born Oppenheimer approximation

clear all;
% initialization
Z=1;S=1;A=0;F=0;V=0;D=0;g=0;Vecp=0;Vec=0;Val=0;EVal=0;
for y=1:41
clear T;S;A;F;V;D;g;Vecp;Vec;Val;EVal;
% y = 11;
disp('Step'); disp(y);
r = 0.45+0.05*y; % distance between nucleii in a.u.(units of
a0, ie. Bohr radius)... since the problem is essentially 1-D, this
is all that is needed
disp('H-H bondlength'); disp(r);
NNr=1/r;
% alphas for the 4 Gaussian basis functions for each H atom
alpha1 = [13.00773 1.962079 0.444529 0.1219492];
alpha = [alpha1 alpha1];
asize=size(alpha);
% one H nucleus at origin, the other at r
ra=[0 0 0 0 r r r r]; % the location of the atom with the ith
basisfunction
% first 4 basis fns come from the atom at origin
% the next 4 come from the one at r
% the S (overlap), T (K.E.) and A (Coulomb) matrices
for i=1:8 % run over all basis functions
for j=1:i % do not run over all basis functions to exploit
symmetry
% intermediate variables
as = alpha(i)+alpha(j);
ap = alpha(i)*alpha(j);
rat=ap/as;
% location of the gaussian resulting from product of
% the 2 gaussian basis functions
rp=(alpha(i)*ra(i)+alpha(j)*ra(j))/as;
S(i,j)=(pi/as)^1.5*exp(-rat*(ra(i)-ra(j))^2);
S(j,i)=S(i,j); % using symmetry
T(i,j)=0.5*rat*(6-4*rat*(ra(i)-ra(j))^2)*S(i,j);
T(j,i)=T(i,j); % using symmetry
if (rp==0)
F0=1+sqrt(pi)/2*erf(sqrt(as*(rpr)^2))/sqrt(as*(rp-r)^2);
elseif (rp==r)
F0=sqrt(pi)/2*erf(sqrt(as*(rp-0)^2))/sqrt(as*(rp0)^2)+1;
else
F0=sqrt(pi)/2*(erf(sqrt(as*(rp-0)^2))/sqrt(as*(rp0)^2)+erf(sqrt(as*(rp-r)^2))/sqrt(as*(rp-r)^2));
end
A(i,j)=-2*pi*Z/as*exp(-rat*(ra(i)-ra(j))^2)*F0;
A(j,i)=A(i,j); % using symmetry
end
end
S
T
A

[V,D]=eig(S); % gives eigenvectors in columns of V, this

diagnolizes S
for i=1:asize(2)
V(:,i)=V(:,i)/(D(i,i)^0.5);
end
% the two-electron integrals P taking care of all symmetries
% it is noted that the gaussian functions evaluate to REAL values
% and the g operator is real and symmetric w.r.t. 1 and 2
for i=1:8
for j=1:i % do not run over all basis functions to exploit
symmetry
as1=alpha(i)+alpha(j);
ap1=alpha(i)*alpha(j);
rp=(alpha(i)*ra(i)+alpha(j)*ra(j))/as1;
for k=1:i-1 % do not run over all basis functions to exploit
symmetry
for l=1:k % do not run over all basis functions to exploit
symmetry
as2=alpha(k)+alpha(l);
ap2=alpha(k)*alpha(l);
rq=(alpha(k)*ra(k)+alpha(l)*ra(l))/as2;
if ((rp-rq)==0)
F0=1;
else
F0=sqrt(pi)/2*erf(sqrt(as1*as2*(rp-rq)^2/
(as1+as2)))/sqrt(as1*as2*(rp-rq)^2/(as1+as2));
end
g(i,j,k,l)=2*pi^2.5/as1/as2/
(as1+as2)^0.5*exp(-ap1*(ra(i)-ra(j))^2/as1-ap2*(ra(k)ra(l))^2/as2)*F0;
g(k,l,i,j)=g(i,j,k,l); % using symmetry
g(j,i,k,l)=g(i,j,k,l); % using symmetry
g(i,j,l,k)=g(i,j,k,l); % using symmetry
g(j,i,l,k)=g(i,j,k,l); % using symmetry
g(k,l,j,i)=g(i,j,k,l); % using symmetry
g(l,k,i,j)=g(i,j,k,l); % using symmetry
g(l,k,j,i)=g(i,j,k,l); % using symmetry
end
k=i;
for l=1:j
as2=alpha(k)+alpha(l);
ap2=alpha(k)*alpha(l);
rq=(alpha(k)*ra(k)+alpha(l)*ra(l))/as2;
if ((rp-rq)==0)
F0=1;
else
F0=sqrt(pi)/2*erf(sqrt(as1*as2*(rp-rq)^2/
(as1+as2)))/sqrt(as1*as2*(rp-rq)^2/(as1+as2));
end
g(i,j,k,l)=2*pi^2.5/as1/as2/
(as1+as2)^0.5*exp(-ap1*(ra(i)-ra(j))^2/as1-ap2*(ra(k)ra(l))^2/as2)*F0;
g(k,l,i,j)=g(i,j,k,l); % using symmetry
g(j,i,k,l)=g(i,j,k,l); % using symmetry
g(i,j,l,k)=g(i,j,k,l); % using symmetry
g(j,i,l,k)=g(i,j,k,l); % using symmetry

g(k,l,j,i)=g(i,j,k,l); % using symmetry

g(l,k,i,j)=g(i,j,k,l); % using symmetry
g(l,k,j,i)=g(i,j,k,l); % using symmetry

end
end
end
end
% Self-consistent loop
C=ones(1,asize(2)); %initial guess
nor=C*S*C'
disp('Initial Guess');
C=C/nor
Elast=1;
EVal=0;
P=C'*C;
count=0;
rplot=-2:0.01:3; % range in atomic units (bohr) for plotting
the probability density
% figure();
% Generating Fock matrix
while((abs(EVal(1)-Elast))>0.000001)
count=count+1;
disp('Step #');
disp(count);
Elast=EVal(1)
for i=1:8
for j=1:8
J=0;
for k=1:8
for l=1:8
J=J+P(k,l)*g(i,j,k,l);
end
end
F(i,j)=T(i,j)+A(i,j)+J;
end
end
% solve the generalized eigenvalue problem FC=ESC
% inverse of V is its conjugate transpose because V is unitary
Fp=V'*F*V; % modified Fock matrix
[Vecp,Val]=eig(Fp);
Vec=V*Vecp;
EigVal=diag(Val,0)
[EVal,index]=sort(EigVal);
disp('Ground State eigenvalue from this step is (in a.u.,
i.e. Hartree):');
Erec(count)=EVal(1) % lowest eigenvalue
GrCoeff=Vec(:,index(1)); % eigenvector corresponding to
ground state
disp('C matrix from this step is:');
C=GrCoeff.' %new C matrix, this is normalized w.r.t. S ie.
C*S*C'=1
disp('Input density matrix for next step is:');
P=0.8*P+0.2*C'*C %new input density matrix
GndWvFn=C(1:4)*exp(-(alpha(1:4)).'*(rplot.*rplot))
+C(5:8)*exp(-(alpha(5:8)).'*((rplot-r).*(rplot-r))); % ground
state wavefunction from STO-4G approximation

%
Uncomment the next 4 lines if you need a plot of probability
with step of convergence
%
hold on;
%
plot(rplot,(abs(GndWvFn)).^2,'r--','LineWidth',1.5);
%
xlabel('r position');
%
ylabel('Probability density');
%
title('Plot of the probability density vs. r position with
step of convergence');
end
Qs=0;
for i=1:8
for j=1:8
for k=1:8
for l=1:8
Qs=Qs+g(i,j,k,l)*C(i)*C(j)*C(k)*C(l);
end
end
end
end
disp('The final total energy (including nuclear-nuclear
repulsion) after convergence for this H-H bond is ');
Eg(y)=2*C*(T+A)*C'+Qs+NNr; % the energy from h for each e, the
e-e interaction and the nucleus-nucleus interaction added
disp(Eg(y));
if Eg(y)==min(Eg)
rmin = r;
Erecmin = Erec;
WvFnmin = GndWvFn;
end
end
figure();
plot([0.5:0.05:2.5],Eg,'bo','LineWidth',2);
title('Plot showing total energy from Hartree Fock treatment of HH using Born Oppenheimer approximation');
xlabel('H-H bondlength');
ylabel('Total energy (in a.u.)');
grid on;
disp('The least energy bond length (A) for H-H is ');
disp(rmin*0.529177);
disp('The energy (Hartree) of this bond is '); disp(min(Eg));
figure();
plot(Erecmin,'ro','LineWidth',2);
axis([1 count min(Erecmin) max(Erecmin)+0.1]);
title('Plot showing convergence of Fock level with every step for
the least energy H-H bondlength');
xlabel('Step of convergence');
ylabel('Fock energy level (in a.u.)');
grid on;
%plot of final probabiliy density
figure();
plot(rplot,(abs(WvFnmin)).^2,'LineWidth',2.5);

xlabel('r position');
ylabel('Probability density');
title('Plot of the probability density of electrons vs. r position
for the least energy H-H bond');
axis tight;
grid on;
%print result