TY - JOUR

T1 - On the construction of diabatic and adiabatic potential energy surfaces based on ab initio valence bond theory

AU - Song, Lingchun

AU - Gao, Jiali

PY - 2008/12/18

Y1 - 2008/12/18

N2 - A theoretical model is presented for deriving effective diabatic states based on ab initio valence bond selfconsistent field (VBSCF) theory by reducing the multiconfigurational VB Hamiltonian into an effective twostate model. We describe two computational approaches for the optimization of the effective diabatic configurations, resulting in two ways of interpreting such effective diabatic states. In the variational diabatic configuration (VDC) method, the energies of the diabatic states are variationally minimized. In the consistent diabatic configuration (CDC) method, both the configuration coefficients and orbital coefficients are simultaneously optimized to minimize the adiabatic ground-state energy in VBSCF calculations. In addition, we describe a mixed molecular orbital and valence bond (MOVB) approach to construct the CDC diabatic and adiabatic states for a chemical reaction. Note that the VDC-MOVB method has been described previously. Employing the symmetric SN2 reaction between NH3 and CH3NH3+ as a test system, we found that the results from ab initio VBSCF and from ab initio MOVB calculations using the same basis set are in good agreement, suggesting that the computationally efficient MOVB method is a reasonable model for VB simulations of condensed phase reactions. The results indicate that CDC and VDC diabatic states converge, respectively, to covalent and ionic states as the molecular geometries are distorted from the minimum of the respective diabatic state along the reaction coordinate. Furthermore, the resonance energy that stabilizes the energy of crossing between the two diabatic states, resulting in the transition state of the adiabatic ground-state reaction, has a strong dependence on the overlap integral between the two diabatic states and is a function of both the exchange integral and the total diabatic ground-state energy.

AB - A theoretical model is presented for deriving effective diabatic states based on ab initio valence bond selfconsistent field (VBSCF) theory by reducing the multiconfigurational VB Hamiltonian into an effective twostate model. We describe two computational approaches for the optimization of the effective diabatic configurations, resulting in two ways of interpreting such effective diabatic states. In the variational diabatic configuration (VDC) method, the energies of the diabatic states are variationally minimized. In the consistent diabatic configuration (CDC) method, both the configuration coefficients and orbital coefficients are simultaneously optimized to minimize the adiabatic ground-state energy in VBSCF calculations. In addition, we describe a mixed molecular orbital and valence bond (MOVB) approach to construct the CDC diabatic and adiabatic states for a chemical reaction. Note that the VDC-MOVB method has been described previously. Employing the symmetric SN2 reaction between NH3 and CH3NH3+ as a test system, we found that the results from ab initio VBSCF and from ab initio MOVB calculations using the same basis set are in good agreement, suggesting that the computationally efficient MOVB method is a reasonable model for VB simulations of condensed phase reactions. The results indicate that CDC and VDC diabatic states converge, respectively, to covalent and ionic states as the molecular geometries are distorted from the minimum of the respective diabatic state along the reaction coordinate. Furthermore, the resonance energy that stabilizes the energy of crossing between the two diabatic states, resulting in the transition state of the adiabatic ground-state reaction, has a strong dependence on the overlap integral between the two diabatic states and is a function of both the exchange integral and the total diabatic ground-state energy.

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U2 - 10.1021/jp803050e

DO - 10.1021/jp803050e

M3 - Article

C2 - 18828577

AN - SCOPUS:58149166598

VL - 112

SP - 12925

EP - 12935

JO - Journal of Physical Chemistry A

JF - Journal of Physical Chemistry A

SN - 1089-5639

IS - 50

ER -