Analytic First-Order Derivatives of Partially Contracted N-Electron Valence State Second-Order Perturbation Theory (PC-NEVPT2)

Abstract

A balanced treatment of dynamic and static electron correlation is important in computational chemistry, and multireference perturbation theory (MRPT) is able to do this at a reasonable computational cost. In this paper, analytic first-order derivatives, speci cally gradients and dipole moments, are developed for a particular MRPT method, state-specific partially contracted n-electron valence state second-order perturbation theory (PC-NEVPT2). Only one linear equation needs to be solved for the derivative calculation if the Z-vector method is employed, which facilitates the practical application of this approach. Comparison of the calculated results with experimental geometrical parameters of O<sub>3</sub> indicates excellent agreement, although the calculated results for O<sub>3</sub><sup>-</sup> are slightly outside the experimental error bars. The 0-0 transition energies of various methylpyrimidines and trans-polyacetylene are calculated by performing geometry optimizations and seminumerical second-order geometrical derivative calculations. In particular, the deviations of 0-0 transition energies of trans-polyacetylene from experimental values are consistently less than 0.1 eV with PC-NEVPT2, indicating the reliability of the method. These results demonstrate the importance of adding dynamic electron correlation on top of methods dominated by static electron correlation and of developing analytic derivatives for highly accurate methods.