On the accuracy of retinal protonated Schiff base models

ABSTRACT

We investigate the molecular geometries of the ground state and the minimal energy conical intersections between the ground and first excited states of the models for the retinal protonated Schiff base in the gas phase using the extended multistate complete active space second-order perturbation theory (XMS-CASPT2). The biggest model in this work is the rhodopsin chromophore truncated between the ε and δ carbon atoms, which consists of 54 atoms and 12-orbital π conjugation. The results are compared with those obtained by the state-averaged complete active space self-consistent field (SA-CASSCF). The XMS-CASPT2 results suggest that the minimum energy conical intersection associated with the so-called 13–14 isomerisation is thermally inaccessible, which is in contrast to the SA-CASSCF results. The differences between the geometries of the conical intersections computed by SA-CASSCF and XMS-CASPT2 are ascribed to the fact that the charge transfer states are more stabilised by dynamical electron correlation than the diradicaloid states. The impact of the various choices of active spaces, basis sets and state-averaging schemes is also examined.

GRAPHICAL ABSTRACT

KEYWORDS:

• RPSB
• CASPT2
• conical intersection
• retinal
• CASSCF

Acknowledgments

This article is part of the special issue in honour of the 80th birthday of Professor Michael Baer. We are grateful to the Air Force Office of Scientific Research Young Investigator Program (Grant No. FA9550-15-1-0031) for generous financial support. The development of the programme infrastructure has been in part supported by National Science Foundation [ACI-1550481 (JWP) and CHE-1351598 (TS)].

Disclosure statement

No potential conflict of interest was reported by the authors.

Additional information

Funding

Air Force Office of Scientific Research [grant number FA9550-15-1-0031]; National Science Foundation [grant number ACI-1550481], [grant number CHE-1351598].