TY - JOUR

T1 - Analytical energy gradients for explicitly correlated wave functions. I. Explicitly correlated second-order Møller-Plesset perturbation theory

AU - Gyorffy, Werner

AU - Knizia, Gerald

AU - Werner, Hans Joachim

N1 - Funding Information:
This work has been supported by the European Research Council Advanced Grant No. 320723 (ASES).
Publisher Copyright:
© 2017 Author(s).

PY - 2017/12/7

Y1 - 2017/12/7

N2 - We present the theory and algorithms for computing analytical energy gradients for explicitly correlated second-order Møller-Plesset perturbation theory (MP2-F12). The main difficulty in F12 gradient theory arises from the large number of two-electron integrals for which effective two-body density matrices and integral derivatives need to be calculated. For efficiency, the density fitting approximation is used for evaluating all two-electron integrals and their derivatives. The accuracies of various previously proposed MP2-F12 approximations [3C, 3C(HY1), 3∗C(HY1), and 3∗A] are demonstrated by computing equilibrium geometries for a set of molecules containing first- and second-row elements, using double-ζ to quintuple-ζ basis sets. Generally, the convergence of the bond lengths and angles with respect to the basis set size is strongly improved by the F12 treatment, and augmented triple-ζ basis sets are sufficient to closely approach the basis set limit. The results obtained with the different approximations differ only very slightly. This paper is the first step towards analytical gradients for coupled-cluster singles and doubles with perturbative treatment of triple excitations, which will be presented in the second part of this series.

AB - We present the theory and algorithms for computing analytical energy gradients for explicitly correlated second-order Møller-Plesset perturbation theory (MP2-F12). The main difficulty in F12 gradient theory arises from the large number of two-electron integrals for which effective two-body density matrices and integral derivatives need to be calculated. For efficiency, the density fitting approximation is used for evaluating all two-electron integrals and their derivatives. The accuracies of various previously proposed MP2-F12 approximations [3C, 3C(HY1), 3∗C(HY1), and 3∗A] are demonstrated by computing equilibrium geometries for a set of molecules containing first- and second-row elements, using double-ζ to quintuple-ζ basis sets. Generally, the convergence of the bond lengths and angles with respect to the basis set size is strongly improved by the F12 treatment, and augmented triple-ζ basis sets are sufficient to closely approach the basis set limit. The results obtained with the different approximations differ only very slightly. This paper is the first step towards analytical gradients for coupled-cluster singles and doubles with perturbative treatment of triple excitations, which will be presented in the second part of this series.

UR - http://www.scopus.com/inward/record.url?scp=85037538407&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85037538407&partnerID=8YFLogxK

U2 - 10.1063/1.5003065

DO - 10.1063/1.5003065

M3 - Article

C2 - 29221401

AN - SCOPUS:85037538407

SN - 0021-9606

VL - 147

JO - Journal of Chemical Physics

JF - Journal of Chemical Physics

IS - 21

M1 - 214101

ER -