TY - JOUR

T1 - Second-order many-body perturbation expansions of vibrational Dyson self-energies

AU - Hermes, Matthew R.

AU - Hirata, So

PY - 2013/11/19

Y1 - 2013/11/19

N2 - Second-order many-body perturbation theories for anharmonic vibrational frequencies and zero-point energies of molecules are formulated, implemented, and tested. They solve the vibrational Dyson equation self-consistently by taking into account the frequency dependence of the Dyson self-energy in the diagonal approximation, which is expanded in a diagrammatic perturbation series up to second order. Three reference wave functions, all of which are diagrammatically size consistent, are considered: the harmonic approximation and diagrammatic vibrational self-consistent field (XVSCF) methods with and without the first-order Dyson geometry correction, i.e., XVSCF[n] and XVSCF(n), where n refers to the truncation rank of the Taylor-series potential energy surface. The corresponding second-order perturbation theories, XVH2(n), XVMP2[n], and XVMP2(n), are shown to be rigorously diagrammatically size consistent for both total energies and transition frequencies, yield accurate results (typically within a few cm-1 at n = 4 for water and formaldehyde) for both quantities even in the presence of Fermi resonance, and have access to fundamentals, overtones, and combinations as well as their relative intensities as residues of the vibrational Green's functions. They are implemented into simple algorithms that require only force constants and frequencies of the reference methods (with no basis sets, quadrature, or matrix diagonalization at any stage of the calculation). The rules for enumerating and algebraically interpreting energy and self-energy diagrams are elucidated in detail.

AB - Second-order many-body perturbation theories for anharmonic vibrational frequencies and zero-point energies of molecules are formulated, implemented, and tested. They solve the vibrational Dyson equation self-consistently by taking into account the frequency dependence of the Dyson self-energy in the diagonal approximation, which is expanded in a diagrammatic perturbation series up to second order. Three reference wave functions, all of which are diagrammatically size consistent, are considered: the harmonic approximation and diagrammatic vibrational self-consistent field (XVSCF) methods with and without the first-order Dyson geometry correction, i.e., XVSCF[n] and XVSCF(n), where n refers to the truncation rank of the Taylor-series potential energy surface. The corresponding second-order perturbation theories, XVH2(n), XVMP2[n], and XVMP2(n), are shown to be rigorously diagrammatically size consistent for both total energies and transition frequencies, yield accurate results (typically within a few cm-1 at n = 4 for water and formaldehyde) for both quantities even in the presence of Fermi resonance, and have access to fundamentals, overtones, and combinations as well as their relative intensities as residues of the vibrational Green's functions. They are implemented into simple algorithms that require only force constants and frequencies of the reference methods (with no basis sets, quadrature, or matrix diagonalization at any stage of the calculation). The rules for enumerating and algebraically interpreting energy and self-energy diagrams are elucidated in detail.

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U2 - 10.1063/1.4813123

DO - 10.1063/1.4813123

M3 - Article

AN - SCOPUS:84903362146

SN - 0021-9606

VL - 139

JO - Journal of Chemical Physics

JF - Journal of Chemical Physics

IS - 3

M1 - 034111

ER -