Elementary electron transfer reactions: from basic concepts to recent computational advances

Abstract

Elementary electron transfer reactions: from basic concepts to recent computational advances / Raffaele Borrelli;Andrea Peluso. March 5, 2013AbstractThe basic chemico-physical concepts and the most recent developments in the dynamics of the elementary electron transfer reactions are reviewed, posing particular attention to discrete state approaches, which combine use of a few experimental data with reliable ab initio calculations of the equilibrium nuclear configurations and normal coordinates of vibration of the redox partners.

Quantum Dynamics of Radiationless Electronic Transitions Including Normal Modes Displacements and Duschinsky Rotations: A Second-Order Cumulant Approach

“…[35][36][37][38][39][40] The coupling operator V AF is in general a function of the vibrational coordinates of the system, although it is quite common to assume its value constant, since electronic transitions take place in a restricted region of the nuclear coordinates. 41 Another approximation of V AF , widely used in the study of photoexcited decays where conical intersections play a major role, is the so called linear vibronic model 1,42,43 in which the coupling operator is a linear function of the nuclear coordinates. In this paper we will develop a formalism which can handle both cases.…”

Theoretical and experimental determination of the absorption and emission spectra of a prototypical indolenine-based squaraine dye

“…1,2 Fast growing research fields such as organic LED technology 3 and dye-sensitized solar cells (DSSC), 4 would strongly benefit from the application of robust and easy-to-use methodologies for the simulation of spectral lineshapes of organic dyes. The research in this field is quickly growing [5][6][7][8][9][10][11][12][13][14][15][16][17][18][19][20][21] (see also Borrelli et al 22 for a recent review) but standardize procedures have not yet been established, and specific computational strategies must be carefully designed and require validation and testing on several class of molecules. [23][24][25][26] In this paper we apply state of the art tools of computational spectroscopy to simulate the absorption and emission lineshapes of squaraine dyes in solution.…”

Vibronic couplings and coherent electron transfer in bridged systems

“…We attribute that peculiar behavior 27,104,113,114 . In all FC calculations, the curvilinear coordinate representation of the normal modes has been adopted to prevent that a large displacement of an angular coordinate could reflect into large shifts of the equilibrium positions of the involved bond distances.…”

“…??, using the density of states evaluated at 298 K including the whole set of normal modes of both redox partners. 27,99,104 .…”