Quantum Calculations in Solution for Large to Very Large Molecules: A New Linear Scaling QM/Continuum Approach.
We present a new implementation of continuum solvation models for semiempirical Hamiltonians that allows the description of environmental effects on very large molecular systems. In this approach based on a domain decomposition strategy of the COSMO model (ddCOSMO), the solution to the COSMO equations is no longer the computational bottleneck but becomes a negligible part of the overall computation time. In this Letter, we analyze the computational impact of COSMO on the solution of the SCF equations for large to very large molecules, using semiempirical Hamiltonians, for both the new ddCOSMO implementation and the most recent, linear scaling one, based on the fast multipole method. A further analysis is on the simulation of the UV/visible spectrum of a light-harvesting pigment-protein complex. All of the results show how the new ddCOSMO algorithm paves the way to routine computations for large molecular systems in the condensed phase.
†Laboratoire Jacques-Louis Lions, Sorbonne Universités, UPMC Univ. Paris 06, UMR 7598, F-75005 Paris, France.|‡Laboratoire de Chimie Théorique, Sorbonne Universités, UPMC Univ. Paris 06, UMR 7616, F-75005 Paris, France.|¶Institut du Calcul et de la Simulation, Sorbonne Universités, UPMC Univ. Paris 06, F-75005 Paris, France.
Filippo
F
Lipparini
¶Institut du Calcul et de la Simulation, Sorbonne Universités, UPMC Univ. Paris 06, F-75005 Paris, France.
Louis
L
Lagardère
§Gaussian, Inc., 340 Quinnipiac Street, Building 40, Wallingford, Connecticut 06492, United States.
Giovanni
G
Scalmani
†Laboratoire Jacques-Louis Lions, Sorbonne Universités, UPMC Univ. Paris 06, UMR 7598, F-75005 Paris, France.|∥CNRS, UMR 7598 and 7616, F-75005 Paris, France.
Benjamin
B
Stamm
Eric
E
Cancès
†Laboratoire Jacques-Louis Lions, Sorbonne Universités, UPMC Univ. Paris 06, UMR 7598, F-75005 Paris, France.|#Institut Universitaire de France, France.|∇Division of Applied Maths, Brown University, Providence, Rhode Island 02912, United States.
Yvon
Y
Maday
†Laboratoire Jacques-Louis Lions, Sorbonne Universités, UPMC Univ. Paris 06, UMR 7598, F-75005 Paris, France.|∥CNRS, UMR 7598 and 7616, F-75005 Paris, France.
Jean-Philip
JP
Piquemal
§Gaussian, Inc., 340 Quinnipiac Street, Building 40, Wallingford, Connecticut 06492, United States.
Michael J
MJ
Frisch
◆Dipartimento di Chimica e Chimica Industriale, Università di Pisa, Via Risorgimento 35, 56126 Pisa, Italy.
Benedetta
B
Mennucci
computational spectroscopy; continuum solvation; domain decomposition; fast algorithms; multiscale methods; quantum chemistry