Lack of evidence for phase-only control of retinal photoisomerization in the strict one-photon limit

Journal article

The concept of shaping electric fields to steer light-induced processes coherently has fascinated scientists for decades. Despite early theoretical considerations that ruled out one-photon coherent control (CC), several experimental studies reported that molecular responses are sensitive to the shape of the excitation field in the weak-field limit. These observations were largely attributed to the presence of rapid-decay channels, but experimental verification is lacking. Here, we test this hypothesis by investigating the degree of achievable control over the photoisomerization of the retinal protonated Schiff-base in bacteriorhodopsin, isorhodopsin and rhodopsin, all of which exhibit similar chromophores but different isomerization yields and excited-state lifetimes. Irrespective of the system studied, we find no evidence for dissipation-dependent behaviour, nor for any CC in the strict one-photon limit. Our results question the extent to which a photochemical process at ambient conditions can be controlled at the amplitude level, and how the underlying molecular potential-energy surfaces and dynamics may influence this controllability.

Authors: Liebel, M; Kukura, P

• Publication status: Published
• Peer review status: Peer reviewed
• Publisher: Nature Publishing Group
• Journal: Nature Chemistry
• Volume: 9
• Issue: 1
• Pages: 45–49
• Publication date: 2016-09-12
• Acceptance date: 2016-07-19
• DOI: 10.1038/nchem.2598
• EISSN: 1755-4349
• ISSN: 1755-4330
• Keywords: photochemistry; chemical physics