Correlated electron-nuclear dynamics with conditional wave functions

Physical Review Letters 113, 083003 (5 pp.) (2014)

Correlated electron-nuclear dynamics with conditional wave functions

Guillermo Albareda, Heiko Appel, Ignacio Franco, Ali Abedi,, Angel Rubio

The molecular Schr\"odinger equation is rewritten in terms of non-unitary equations of motion for the nuclei (or electrons) that depend parametrically on the configuration of an ensemble of generally defined electronic (or nuclear) trajectories. This scheme is exact and does not rely on the tracing-out of degrees of freedom. Hence, the use of trajectory-based statistical techniques can be exploited to circumvent the calculation of the computationally demanding Born-Oppenheimer potential-energy surfaces and non-adiabatic coupling elements. The concept of potential-energy surface is restored by establishing a formal connection with the exact factorization of the full wave function. This connection is used to gain insight from a simplified form of the exact propagation scheme.

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We gratefully acknowledge John C. Tully and Xavier Oriols for useful conversations. G. A. acknowledges the Beatriu de Pinós Program for financial support through Project No. 2010BP-A00069. I. F. thanks the Alexander von Humboldt Foundation for financial support. A. R. acknowledges support by the European Research Council Advanced Grant DYNamo (No. ERC-2010-AdG-267374), a Spanish Grant (No. FIS2010- 21282-C02-01), Grupos Consolidados UPV/EHU del Gobierno Vasco (IT-578-13), and the Ikerbasque and European Commission Project CRONOS (Grant No. 280879- 2).

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