TY - JOUR

T1 - Linear-scaling generation of potential energy surfaces using a double incremental expansion

AU - König, C.

AU - Christiansen, O.

N1 - Funding information: C.K. acknowledges funding by a Feodor-Lynen research fellowship from the Alexander von Humboldt Foundation as well as a post-doctoral grant from the Carlsberg Foundation. O.C. acknowledges support from the Lundbeck Foundation, the Danish e-infrastructure Cooperation (DeiC), and the Danish Council for Independent Research through a Sapere Aude III Grant (No. DFF-4002-00015).

PY - 2016/8/14

Y1 - 2016/8/14

N2 - We present a combination of the incremental expansion of potential energy surfaces (PESs), known as n-mode expansion, with the incremental evaluation of the electronic energy in a many-body approach. The application of semi-local coordinates in this context allows the generation of PESs in a very cost-efficient way. For this, we employ the recently introduced flexible adaptation of local coordinates of nuclei (FALCON) coordinates. By introducing an additional transformation step, concerning only a fraction of the vibrational degrees of freedom, we can achieve linear scaling of the accumulated cost of the single point calculations required in the PES generation. Numerical examples of these double incremental approaches for oligo-phenyl examples show fast convergence with respect to the maximum number of simultaneously treated fragments and only a modest error introduced by the additional transformation step. The approach, presented here, represents a major step towards the applicability of vibrational wave function methods to sizable, covalently bound systems.

AB - We present a combination of the incremental expansion of potential energy surfaces (PESs), known as n-mode expansion, with the incremental evaluation of the electronic energy in a many-body approach. The application of semi-local coordinates in this context allows the generation of PESs in a very cost-efficient way. For this, we employ the recently introduced flexible adaptation of local coordinates of nuclei (FALCON) coordinates. By introducing an additional transformation step, concerning only a fraction of the vibrational degrees of freedom, we can achieve linear scaling of the accumulated cost of the single point calculations required in the PES generation. Numerical examples of these double incremental approaches for oligo-phenyl examples show fast convergence with respect to the maximum number of simultaneously treated fragments and only a modest error introduced by the additional transformation step. The approach, presented here, represents a major step towards the applicability of vibrational wave function methods to sizable, covalently bound systems.

UR - http://www.scopus.com/inward/record.url?scp=84982156270&partnerID=8YFLogxK

U2 - 10.1063/1.4960189

DO - 10.1063/1.4960189

M3 - Article

VL - 145

JO - Journal of Chemical Physics

JF - Journal of Chemical Physics

SN - 0021-9606

IS - 6

M1 - 064105

ER -