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

revised on 01.08.2019, 08:18 and posted on 01.08.2019, 15:34 by Yoshio Nishimoto
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 O3 indicates excellent agreement, although the calculated results for O3- 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.


JSPS KAKENHI Grant Number 17K14436


Email Address of Submitting Author


Kyoto University



ORCID For Submitting Author


Declaration of Conflict of Interest

no conflict of interest

Version Notes

revision 1