New Insights into the State Trapping of UV-Excited Thymine

Stojanović, Ljiljana; Bai, Shuming; Nagesh, Jayashree; Izmaylov, Artur F.; Crespo‐Otero, Rachel; Lischka, Hans; Barbatti, Mario

doi:10.3390/molecules21111603

Cited by 39 publications

(77 citation statements)

References 53 publications

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“…Since the publication of the algorithm to evaluate approximate nonadiabatic couplings with CC2 and ADC(2), 263 different groups have used and implemented this methodology. 255,[270][271][272][273][274][275][276][277][278][279][280] So far, most of the ADC(2) NA-MQC dynamics simulations have focused on the photochemistry of heterocycles [270][271][272][273] and the effect of aggregation with water on their excited-state dynamics. [274][275][276][277][278] A recent systematic study of some oligocenes and hetero-atomic fused rings has raised some concerns about the description of the La and Lb states with both CC2 and ADC(2).…”

Section: Linear-response Methods I: CC Adcmentioning

confidence: 99%

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Recent Advances and Perspectives on Nonadiabatic Mixed Quantum–Classical Dynamics

2018

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Nonadiabatic mixed quantum-classical (NA-MQC) dynamics methods form a class of computational theoretical approaches in quantum chemistry tailored to investigate the time evolution of nonadiabatic phenomena in molecules and supramolecular assemblies. NA-MQC is characterized by a partition of the molecular system into two subsystems: one to be treated quantum mechanically (usually but not restricted to electrons) and another to be dealt with classically (nuclei). The two subsystems are connected through nonadiabatic couplings terms to enforce self-consistency. A local approximation underlies the classical subsystem, implying that direct dynamics can be simulated, without needing precomputed potential energy surfaces. The NA-MQC split allows reducing computational costs, enabling the treatment of realistic molecular systems in diverse fields. Starting from the three most well-established methods-mean-field Ehrenfest, trajectory surface hopping, and multiple spawning-this review focuses on the NA-MQC dynamics methods and programs developed in the last 10 years. It stresses the relations between approaches and their domains of application. The electronic structure methods most commonly used together with NA-MQC dynamics are reviewed as well. The accuracy and precision of NA-MQC simulations are critically discussed, and general guidelines to choose an adequate method for each application are delivered.

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Section: Linear-response Methods I: CC Adcmentioning

confidence: 99%

“…11 197 Thymine dynamics delivers qualitatively different results with either CASSCF or ADC(2). 255 When we become aware of all this methodological divergence, it is natural to ask where it comes from. Is it a consequence of the specific nonadiabatic dynamics algorithm, or is it due to the electronic structure method?…”

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confidence: 99%

Recent Advances and Perspectives on Nonadiabatic Mixed Quantum–Classical Dynamics

2018

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“…719 Nevertheless, the high computational cost of MR-CISD and the lack of energy gradients for CASPT2 have posed significant impediments to the use of these methods in such simulations. This situation opened space for dynamics based on less demanding multireference approaches, including CASSCF (Cyt, 752,[768][769][770] Thy, 767,768 Ura 767,768,[771][772][773][774] ), MRCIS (Ade, 768,775 Gua 768,776 ), semiempirical OM2/MRCI (Ade, 777 Gua, 778 in investigations of steady properties [781][782][783][784][785] and dynamics [786][787][788][789][790][791] of excited nucleobases and nucleobase derivatives.…”

Section: Nucleobases and Derivativesmentioning

confidence: 99%

Multireference Approaches for Excited States of Molecules

et al. 2018

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Understanding the properties of electronically excited states is a challenging task that becomes increasingly important for numerous applications in chemistry, molecular physics, molecular biology, and materials science. A substantial impact is exerted by the fascinating progress in time-resolved spectroscopy, which leads to a strongly growing demand for theoretical methods to describe the characteristic features of excited states accurately. Whereas for electronic ground state problems of stable molecules the quantum chemical methodology is now so well developed that informed nonexperts can use it efficiently, the situation is entirely different concerning the investigation of excited states. This review is devoted to a specific class of approaches, usually denoted as multireference (MR) methods, the generality of which is needed for solving many spectroscopic or photodynamical problems. However, the understanding and proper application of these MR methods is often found to be difficult due to their complexity and their computational cost. The purpose of this review is to provide an overview of the most important facts about the different theoretical approaches available and to present by means of a collection of characteristic examples useful information, which can guide the reader in performing their own applications.

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“…The experimental lifetime of UV-photexcited thymine, 5-7 ps, is significantly longer than that of other photoexcited nucleobases, 37 and its decay has been extensively studied experimentally [37][38][39][40][41][42][43][44] and computationally. 43,[45][46][47][48][49][50][51][52][53] Nevertheless, the deactivation mechanism of UV-photoexcited thymine remains controversial. 37,45,53 In particular, prior NAMD-SH simulations using multiconfiguration selfconsistent field (MCSCF) and the second-order algebraic diagrammatic construction [ADC (2)] methods lead to excited-state lifetimes hard to reconcile with each other and with ultrafast pump-probe experiments.…”

Section: Introductionmentioning

confidence: 99%