Ultrafast photochemistry of free-base porphyrin: a theoretical investigation of B → Q internal conversion mediated by dark states. Issue 18 (27th April 2018)

• Record Type: Journal Article
• Authors: Falahati, Konstantin; Hamerla, Carsten; Huix-Rotllant, Miquel; Burghardt, Irene
• Is Part Of: Physical chemistry chemical physics. Volume 20:Issue 18(2018)
• Page Start: 12483
• Page End: 12492
• Publication Date: 2018-04-27
• Subjects: Chemistry, Physical and theoretical -- Periodicals; 541.3
• DOI: 10.1039/c8cp00657a
• Languages: English
• ISSNs: 1463-9076

Abstract

Abstract : Ultrafast B → Q internal conversion in free-base porphyrin is mediated by dark states, necessitating a description beyond Gouterman's four-orbital model. Abstract : We examine the mechanism of ultrafast internal conversion between the B band (Soret band) and the Q band in porphine (H2 P), the prototypical free-base porphyrin, using electronic structure studies and on-the-fly surface-hopping nonadiabatic dynamics. Our study highlights the crucial role of dark states within the N band which are found to mediate B/Q state transfer, necessitating a treatment beyond Gouterman's classic four-orbital model. The sequential B → N → Q pathway dominates largely over the direct B → Q pathway which is found to be energetically unfavorable. Potential energy surface cuts and conical intersections between excited states are determined by TDDFT and validated by CASSCF/CASPT2 and XMCQDPT2 calculations. Both the static analysis and on-the-fly surface-hopping calculations suggest a pathway which involves minor structural deformations via in-plane vibrations. The B → N conversion is a barrierless adiabatic process occurring within ∼20 fs, while the subsequent N → Q conversion occurs via a conical intersection within ∼100 fs, in agreement with time-resolved experiments for porphine and related free base porphyrins. Furthermore, evidence for both sequential and direct transfer to the Q x and Q y states is obtained.