TY - JOUR

T1 - Adaptive density-guided approach to double incremental potential energy surface construction

AU - Artiukhin, Denis G.

AU - Klinting, Emil L.

AU - König, Carolin

AU - Christiansen, Ove

N1 - Funding Information: We thank Diana Madsen for providing us with the tetraphenyl and hexaphenyl FALCON coordinates and Leila Dzabbarova for exploratory computations on convergence of double incremental expansions. D.G.A. acknowledges funding from the European Union’s Horizon 2020 research and innovation programme under the Marie Skłodowska–Curie Grant Agreement No. 835776. C.K. acknowledges support from the Deutsche Forschungsgemeinschaft (DFG) through the Emmy Noether Young Group Leader Programme (Project No. KO 5423/1-1). O.C. acknowledges support from the Danish Council for Independent Research through a Sapere Aude III Grant (No. DFF-4002-00015).

PY - 2020/5/21

Y1 - 2020/5/21

N2 - We present a combination of the recently developed double incremental expansion of potential energy surfaces with the well-established adaptive density-guided approach to grid construction. This unique methodology is based on the use of an incremental expansion for potential energy surfaces, known as n-mode expansion; an incremental many-body representation of the electronic energy; and an efficient vibrational density-guided approach to automated determination of grid dimensions and granularity. The reliability of the method is validated calculating potential energy surfaces and obtaining fundamental excitation energies for three moderate-size chain-like molecular systems. The use of our methodology leads to considerable computational savings for potential energy surface construction compared to standard approaches while maintaining a high level of accuracy in the resulting potential energy surfaces. Additional investigations indicate that our method can be applied to covalently bound and strongly interacting molecular systems, even though these cases are known to be very unfavorable for fragmentation schemes. We therefore conclude that the presented methodology is a robust and flexible approach to potential energy surface construction, which introduces considerable computational savings without compromising the accuracy of vibrational spectra calculations.

AB - We present a combination of the recently developed double incremental expansion of potential energy surfaces with the well-established adaptive density-guided approach to grid construction. This unique methodology is based on the use of an incremental expansion for potential energy surfaces, known as n-mode expansion; an incremental many-body representation of the electronic energy; and an efficient vibrational density-guided approach to automated determination of grid dimensions and granularity. The reliability of the method is validated calculating potential energy surfaces and obtaining fundamental excitation energies for three moderate-size chain-like molecular systems. The use of our methodology leads to considerable computational savings for potential energy surface construction compared to standard approaches while maintaining a high level of accuracy in the resulting potential energy surfaces. Additional investigations indicate that our method can be applied to covalently bound and strongly interacting molecular systems, even though these cases are known to be very unfavorable for fragmentation schemes. We therefore conclude that the presented methodology is a robust and flexible approach to potential energy surface construction, which introduces considerable computational savings without compromising the accuracy of vibrational spectra calculations.

UR - http://www.scopus.com/inward/record.url?scp=85090131521&partnerID=8YFLogxK

U2 - 10.1063/5.0004686

DO - 10.1063/5.0004686

M3 - Article

VL - 152

JO - The journal of chemical physics

JF - The journal of chemical physics

SN - 0021-9606

IS - 19

M1 - 194105

ER -