Theoretical Analysis of Exciton Wave Packet Dynamics in Polaritonic Wires

We present a comprehensive study of exciton wave packet evolution in disordered lossless polaritonic wires. Our simulations reveal signatures of ballistic, diffusive, and subdiffusive exciton dynamics under strong light-matter coupling and identify the typical timescales associated with the transitions between these qualitatively distinct transport phenomena. We determine optimal truncations of the molecular subsystem and radiation field required for generating reliable time-dependent data from computational simulations at affordable cost. The time evolution of the photonic part of the wave function reveals that many cavity modes contribute to the dynamics in a non-trivial fashion. Hence, a sizable number of photon modes is needed to describe exciton propagation with reasonable accuracy. We find and discuss an intriguingly common lack of dominance of the photon mode on resonance with the molecular system both in the presence and absence of disorder. We discuss the implications of our investigations to the development of theoretical models and analysis of experiments where coherent intermolecular energy transport and static disorder play an important role

Coupled Cluster Externally Corrected by Adaptive Configuration Interaction

An externally corrected coupled cluster (CC) method, where an adaptive configuration interaction (ACI) wave function provides the external cluster amplitudes, named ACI-CC, is presented. By exploiting the connection between configuration interaction and coupled cluster through cluster analysis, the higher-order T3 and T4 terms obtained from ACI are used to augment the T1 and T2 amplitude equations from traditional coupled cluster. These higher-order contributions are kept frozen during the coupled cluster iterations and do not contribute to an increased cost with respect to CCSD. We have benchmarked this method on three closed-shell systems: beryllium dimer, carbonyl oxide, and cyclobutadiene, with good results compared to other corrected coupled cluster methods. In all cases, the inclusion of these external corrections improved upon the "gold standard" CCSD(T) results, indicating that ACI-CCSD(T) can be used to assess strong correlation effects in a system and as an inexpensive starting point for more complex external corrections

Reinterpreting the infrared spectrum of H plus HCN: Methylene amidogen radical and its coproducts

The methylene amidogen radical (H2CN) plays a role in high-energy material combustion and extrater-resterial atmospheres. Recent theoretical work has struggled to match experimental assignments for its CN and antisymmetric CH2 stretching frequencies (nu(2) and nu(5)), which were reported to occur at 1725 and 3103 cm(-1). Herein, we compute the vibrational energy levels of this molecule by extrapolating quadruples-level coupled-cluster theory to the complete basis limit and adding corrections for vibrational anharmonicity. This level of theory predicts that nu(2) and nu(5) should occur at 1646 and 2892 cm(-1), at odds with the experimental assignments. To investigate the possibility of defects in our theoretical treatment, we analyze the sensitivity of our approach to each of its contributing approximations. Our analysis suggests that the observed deviation from experiment is too large to be explained as an accumulation of errors, leading us to conclude that these transitions were misassigned. To help resolve this discrepancy, we investigate possible byproducts of the H + HCN reaction, which was the source of H2CN in the original experiment. In particular, we predict vibrational spectra for cis-HCNH, trans-HCNH, and H2CNH using high-level coupled-cluster computations. Based on these results, we reassign the transition at 1725 cm(-1) to nu(3) of trans-HCNH, yielding excellent agreement. Supporting this identification, we assign a known contaminant peak at 886 cm(-1) to nu(5) of the same conformer. Our computations suggest that the peak observed at 3103 cm(-1), however, does not belong to any of the aforementioned species. To facilitate further investigation, we use structure and bonding arguments to narrow the range of possible candidates. These arguments lead us to tentatively put forth formaldazine [(H2CN)(2)] as a suggestion for further study, which we support with additional computations. Published by AIP Publishing.Department of Energy, Office of Basic Energy Sciences, Computational and Theoretical Chemistry (CTC) ProgramUniv Georgia, Ctr Computat Quantum Chem, Athens, GA 30602 USAMessiah Coll, Dept Chem & Biochem, Mechanicsburg, PA 17055 USAUniv Fed Sao Paulo, Inst Environm Chem & Pharmaceut Sci, Sao Paulo, BrazilBiola Univ, Dept Chem Phys & Engn, La Mirada, CA 90639 USAUniv Fed Sao Paulo, Inst Environm Chem & Pharmaceut Sci, Sao Paulo, BrazilDepartment of Energy, Office of Basic Energy Sciences, Computational and Theoretical Chemistry (CTC) Program: DE-SC0018412Web of Scienc