Quantum-dynamical Modeling of the Rydberg to Valence Excited-State Internal Conversion in Cyclobutanone and Cyclopentanone

Kuhlman, Thomas Scheby; Sauer, Stephan P. A.; Sølling, Theis I.; Møller, Klaus Braagaard

doi:10.1051/epjconf/20134102033

EPJ Web of Conferences

2013

DOI: 10.1051/epjconf/20134102033

|View full text |Cite

Quantum-dynamical Modeling of the Rydberg to Valence Excited-State Internal Conversion in Cyclobutanone and Cyclopentanone

Thomas Scheby Kuhlman

Stephan P. A. Sauer

Theis I. Sølling

et al.

Abstract: Abstract. In this paper we present 4-state, 5-dimensional Vibronic Coupling Hamiltonians for cyclobutanone and cyclopentanone. Wave packet calculations using these Hamiltonians reveal that for cyclobutanone the (n,3s) to (n,π*) internal conversion involves direct motion in nuclear modes coupling the two states leading to fast population transfer. For cyclopentanone, internal vibrational energy redistribution is a bottleneck for activating reactive nuclear modes leading to slower population transfer.

Help me understand this report

Search citation statements

Order By: Relevance

Paper Sections

Select...

Citation Types

Supporting

Mentioning

Contrasting

Year Published

2024

Publication Types

Select...

Article2

Relationship

Self Cite0

Independent2

Authors

Journals

Cited by 2 publications

References 7 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

The photochemistry of Rydberg-excited cyclobutanone: Photoinduced processes and ground state dynamics

Eng,

Rankine,

Penfold

2024

The Journal of Chemical Physics

View full text Add to dashboard Cite

Owing to ring strain, cyclic ketones exhibit complex excited state dynamics with multiple competing photochemical channels active on the ultrafast timescale. While the excited state dynamics of cyclobutanone after π* ← n excitation into the lowest-energy excited singlet (S1) state has been extensively studied, the dynamics following 3s ← n excitation into the higher-lying singlet Rydberg (S2) state are less well understood. Herein, we employ fully quantum multiconfigurational time-dependent Hartree (MCTDH) simulations using a model Hamiltonian as well as “on-the-fly” trajectory-based surface-hopping dynamics (TSHD) simulations to study the relaxation dynamics of cyclobutanone following 3s ← n excitation and to predict the ultrafast electron diffraction scattering signature of these relaxation dynamics. Our MCTDH and TSHD simulations indicate that relaxation from the initially-populated singlet Rydberg (S2) state occurs on the timescale of a few hundreds of femtoseconds to a picosecond, consistent with the symmetry-forbidden nature of the state-to-state transition involved. There is no obvious involvement of excited triplet states within the timeframe of our simulations (<2 ps). After non-radiative relaxation to the electronic ground state (S0), vibrationally hot cyclobutanone has sufficient internal energy to form multiple fragmented products including C2H4 + CH2CO (C2; 20%) and C3H6 + CO (C3; 2.5%). We discuss the limitations of our MCTDH and TSHD simulations, how these may influence the excited state dynamics we observe, and—ultimately—the predictive power of the simulated experimental observable.

show abstract

The photochemistry of Rydberg-excited cyclobutanone: Photoinduced processes and ground state dynamics

Eng,

Rankine,

Penfold

2024

The Journal of Chemical Physics

View full text Add to dashboard Cite

show abstract

Prediction through quantum dynamics simulations: Photo-excited cyclobutanone

Bennett,

Freibert,

Spinlove

et al. 2024

The Journal of Chemical Physics

View full text Add to dashboard Cite

Quantum dynamics simulations are becoming a standard tool for simulating photo-excited molecular systems involving a manifold of coupled states, known as non-adiabatic dynamics. While these simulations have had many successes in explaining experiments and giving details of non-adiabatic transitions, the question remains as to their predictive power. In this work, we present a set of quantum dynamics simulations on cyclobutanone using both grid-based multi-configuration time-dependent Hartree and direct dynamics variational multi-configuration Gaussian methods. The former used a parameterized vibronic coupling model Hamiltonian, and the latter generated the potential energy surfaces on the fly. The results give a picture of the non-adiabatic behavior of this molecule and were used to calculate the signal from a gas-phase ultrafast electron diffraction (GUED) experiment. Corresponding experimental results will be obtained and presented at a later stage for comparison to test the predictive power of the methods. The results show that over the first 500 fs after photo-excitation to the S2 state, cyclobutanone relaxes quickly to the S1 state, but only a small population relaxes further to the S0 state. No significant transfer of population to the triplet manifold is found. It is predicted that the GUED experiments over this time scale will see signals related mostly to the C–O stretch motion and elongation of the molecular ring along the C–C–O axis.

show abstract

scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.

Contact Info

customersupport@researchsolutions.com

10624 S. Eastern Ave., Ste. A-614

Henderson, NV 89052, USA

This site is protected by reCAPTCHA and the Google Privacy Policy and Terms of Service apply.

Blog Terms and Conditions API Terms Privacy Policy Contact Cookie Preferences Do Not Sell or Share My Personal Information

Made with 💙 for researchers

Part of the Research Solutions Family.

Quantum-dynamical Modeling of the Rydberg to Valence Excited-State Internal Conversion in Cyclobutanone and Cyclopentanone

Cited by 2 publications

References 7 publications

The photochemistry of Rydberg-excited cyclobutanone: Photoinduced processes and ground state dynamics

The photochemistry of Rydberg-excited cyclobutanone: Photoinduced processes and ground state dynamics

Prediction through quantum dynamics simulations: Photo-excited cyclobutanone

Contact Info

Product

Resources

About