Potential Energy Surfaces C.

David Sherrill School of Chemistry and Biochemistry Georgia Institute of Technology

Potential Energy Surfaces A potential energy surface is a mathematical function that gives the energy of a molecule as a function of its geometry. Molecular Mechanics provides this energy as a function of stretches, bends, torsions, etc. This is an approximate model that breaks down in some situations (e.g., breaking bonds). Only works when parameters are available. Quantum Mechanics provides an energy function which can be exact in principle and works for any molecule. In practice, approximate quantum methods are used due to computational expense.

The Molecular Hamiltonian 1 ZA 1 ZA Z B 2 2 = 1 i A + + , H 2 i i>j rij A 2MA A,i rAi A>B RAB (1) in atomic units, where i, j refer to electrons and A, B refer to nuclei. The Hamiltonian may be written more compactly as H = TN (R) + Te (r) + VeN (r, R) + VN N (R) + Vee (r), (2)

where R is the set of nuclear coordinates and r is the set of electronic coordinates.

Separability Some parts of the Hamiltonian depend on nuclear coordinates R, and others depend on electronic coordinates r. Any time the Hamiltonian is separable like H(q1 , q2 ) = H1 (q1 ) + H2 (q2 ), then the eigenfunctions are just (q1 , q2 ) = 1 (q1 )2 (q2 ) (4) (3)

and the eigenvalues are just E = E1 +E2 , where H1 (q1 )1 (q1 ) = E1 1 (q1 ) and H2 (q2 )2 (q2 ) = E2 2 (q2 ). Unfortunately, the ZA electron-nuclear potential energy VeN (r, R) = A,i rAi prevents our molecular Hamiltonian from being separable.

The Born-Oppenheimer Approximation Try to separate the electronic and nuclear degrees of freedom even though they are coupled by the electron-nuclear potential energy VeN (r, R). We can do this because the electrons are much lighter than the nuclei, and so with respect to the electrons, the nuclei are almost stationary. Thus we 1. Fix the nuclei at some chosen conguration Ra 2. Solve for the motion of the electrons for this nuclear conguration, giving an electronic energy Ee (Ra ) and wavefunction (r; Ra ) 3. Repeat for other nuclear congurations Rb of interest, building up a Potential Energy Surface Ee (R).

Some Mathematical Details Initially, TN (R) can be neglected since TN is smaller than Te by a factor of MA /e , where e is the reduced mass of an electron. Thus for a xed nuclear conguration, we have Hel = Te (r) + VeN (r; R) + VN N (R) + Vee (r) such that He (r; R)(r; R) = Ee (R)(r; R) This is the clamped-nuclei Schrdinger equation. Note o VN N (R) is just a constant for any particular R. (6) (5)

The Total Wavefunction An exact solution to the full Schrdinger equation can be o obtained by using an (innite) expansion of the form (r, R) =
k

k (r; R)k (R),

(7)

although usually only one or two terms are necessary for a particular state. Inserting this expansion into the original Schrdinger equation eventually yields: o
TN + Tkk + Tkk + Ukk E k (R) =

(8)

k =k

Ukk + Tkk + Tkk k (R)

where TN =
A

1 2 , 2MA A

(9) (10) (11) (12)

Tkk (R) =
A Tkk (R)

1 k (r; R)|A |k (r; R) A , MA 1 k (r; R)|2 |k (r; R) , A 2MA

=
A

Ukk (R) = k (r; R)|He |k (r; R) .

The Nuclear Wavefunction Fortunately, the previous expressions involve terms which are usually small, and assuming the wavefunction is real, we normally obtain the following equation for the motion of the nuclei on a given Born-Oppenheimer potential energy surface:
TN + Tkk + Ukk k (R) = Ek (R)

(13)

Thus, when the o-diagonal couplings can be ignored, the nuclei move in a potential eld set up by the electrons. The potential energy at each point is given primarily by Ukk (the expectation value of the electronic energy, just Ee (R) previously), with a small correction factor Tkk , called the Born-Oppenheimer Diagonal Correction (BODC).

The Born-Oppenheimer Diagonal Correction EBODC = (r; R)|Tn |(r; R) , (14)

Also called the adiabatic correction. First systematic study at the Hartree-Fock level by Handy, Yamaguchi, and Schaefer (1986). First systematic study at correlated levels of theory by Valeev and Sherrill (2003).

Table 1: Adiabatic correction to the barrier to linearity of water in the ground state (in cm1 )a Basis cc-pVDZ cc-pVDZ cc-pVDZ cc-pVTZ cc-pVTZ cc-pVQZ
a b

Method RHF CISD CISDT RHF CISD RHF

C2v 600.28 615.03 616.82 596.53 611.89 595.57

Dh 585.20 599.15 600.62 581.43 596.73 580.72

b Ee

-15.08 -15.88 -16.20 -15.10 -15.16 -14.85

Data from Valeev and Sherrill, 2003. The dierence between the adiabatic correction

for the C2v and Dh structures.

Table 2: Adiabatic corrections to bond length and harmonic frequencies of BH, CH+ , and NHa BH re () A e (cm1 )
a

CH+ -2.81

NH 0.00027 -1.38

0.00066 0.00063 -2.25

Data from Temelso, Valeev, and Sherrill, 2004.

Coordinates for Potential Energy Surfaces In the absence of elds, a molecules potential energy doesnt change if it is translated or rotated in space. Thus the potential energy only depends on a molecules internal coordinates. There are 3N total coordinates for a molecule (x, y, z for each atom), minus three translations and three rotations which dont matter (only two rotations for linear molecules). The internal coordinates may be represented by simple stretch, bend, torsion coordinates, or symmetry-adapted linear combinations, or redundant coordinates, or normal modes coordinates, etc.

Characterizing Potential Energy Surfaces The most interesting points on PESs are the stationary points, where the gradients with respect to all internal coordinates are zero. 1. Minima: correspond to stable or quasi-stable species; i.e., reactants, products, intermediates. 2. Transition states: saddle points which are minima in all dimensions but one; a maximum in that dimension. 3. Higher-order saddle points: a minimum in all dimensions but n, where n > 1; maximum in the other n dimensions.

Figure 1: Example PES from Steinfeld, Francisco, and Hase

Figure 2: H2 + H H + H2

Hessian Index The Hessian index is the number of negative eigenvalues of the force constant matrix. For a stationary point, this corresponds to the number of internal degrees of freedom along which that point is a potential energy maximum. The Hessian index is 0 for minima, 1 for transition states, > 1 for higher-order saddle points. The Hessian index also corresponds to the number of imaginary vibrational frequencies. A geometry optimization, when run to completion, will provide a stationary point geometry. Typically, this is a potential energy minimum. However, the optimization might get stuck on a saddle point. A vibrational analysis can verify the nature of the stationary point via the Hessian index.