On the molecular mechanism of non-radiative decay of nitrobenzene and the unforeseen challenges this simple molecule holds for electronic structure theory

Literature Information

Publication Date 2014-05-02
DOI 10.1039/C4CP01232A
Impact Factor 3.676
Authors

Jan-M. Mewes, Vladimir Jovanović, Christel M. Marian, Andreas Dreuw


View Original

Abstract

In this work, we present a complete mechanistic picture of the non-radiative decay of the mono-substituted aromatic compound nitrobenzene from the bright singlet state to the electronic ground state. This mechanism involves internal conversion (IC) and inter-system crossing (ISC) along three dominating internal coordinates of the nitro group and consistently explains the experimental findings. Relaxation from the lowest triplet state via ISC occurs along the out-of-plane bending coordinate of the nitro group, while initial IC as well as ultrafast ISC into the triplet manifold take place along symmetric NO stretching and ONO bending modes that have not been considered yet. The proposed mechanism is based on high-level single- and multi-reference electronic structure calculations employing ADC3, MOM-CCSD(T), EOM-CCSD, DFT/MRCI and CAS-SCF/NEVPT2 levels of theory, which is, as we will demonstrate, absolutely necessary to assure a reliable and sufficiently accurate theoretical description of nitrobenzene. The need for third-order methods will be traced back to the large double-excitation character of about 50% of the second excited singlet state of nitrobenzene. As a result, second-order methods like approximate coupled-cluster of second order (CC2) and partially even (EOM-)CCSD yield a qualitatively wrong picture of the excited states. Surprisingly, already the description of the ground state geometries is problematic at the CC2 and partially also CCSD level of theory.

Related Literature

Electrochromic sensing platform based on steric hindrance effects for CEA detection

Yong Xia, Jing Li, Erkang Wang

2016-04-26 Communication

DOI: 10.1039/C6AN00675B

A miniaturized electrochemical device integrating a biconical microchannel and carbon fiber disk ultramicroelectrode

Fengxia Chang, Xia Xie, Meixian Li, Zhiwei Zhu

2016-07-05 Communication

DOI: 10.1039/C6AN01205A

Engineering DNAzyme cascade for signal transduction and amplification

Jing Li, Ke Quan, Yanjing Yang, Xiaohai Yang, Xiangxian Meng, Jin Huang, Kemin Wang

2020-01-10 Paper

DOI: 10.1039/C9AN02003A

Graphene oxide-based electrochemical label-free detection of glycoproteins down to aM level using a lectin biosensor

L. Klukova, J. Filip, S. Belicky, A. Vikartovska, J. Tkac

2016-05-31 Communication

DOI: 10.1039/C6AN00793G

Spectroelectrochemical and computational studies of tetrahydrocannabinol (THC) and carboxy-tetrahydrocannabinol (THC-COOH)

Shruti D. Bindesri, Ricardo Jebailey, Najwan Albarghouthi, Cory C. Pye, Christa L. Brosseau

2020-01-10 Paper

DOI: 10.1039/C9AN02173F

DNA-fueled molecular machine for label-free and non-enzymatic ultrasensitive detection of telomerase activity

Chaoying Liu, Fang Pu, Jinsong Ren, Xiaogang Qu

2016-07-05 Communication

DOI: 10.1039/C6AN00997B

Effective isolation of exosomes with polyethylene glycol from cell culture supernatant for in-depth proteome profiling

Zhigang Sui, Yichu Shan, Lihua Zhang, Yukui Zhang

2016-05-04 Paper

DOI: 10.1039/C6AN00892E

Contents list

Front/Back Matter

DOI: 10.1039/D0AN90019B

Measurement of serum phosphate levels using a mobile sensor

Sarah Esparza, Dimei Wu, Mark R. Hanudel, Barbara Gales, Isidro B. Salusky

2020-01-10 Paper

DOI: 10.1039/C9AN02215E

You might also like

Compound Q&A

What precautions should be taken when handling lithium chloride hydrate (1:1:1) (CAS: 16712-20-2)?

When handling lithium chloride hydrate (1:1:1) (CAS: 16712-20-2), it is importan...

16712-20-2Lithium chloride hyd...
Compound Q&A

Is 4-(4H-1,2,4-Triazol-4-yl)piperidine (CAS: 690261-92-8) safe?

4-(4H-1,2,4-Triazol-4-yl)piperidine is generally considered safe for use in phar...

690261-92-84-(4H-1,2,4-Triazol-...
Compound Q&A

How should waste containing 1,3-Thiazole-2-carboxamide (CAS: 16733-85-0) be handled?

Waste containing 1,3-Thiazole-2-carboxamide (CAS: 16733-85-0) should be collecte...

16733-85-01,3-Thiazole-2-carbo...
Compound Q&A

What regulatory guidelines apply to 5-(Difluoromethyl)-2-fluorobenzonitrile (CAS: 934175-58-3)?

5-(Difluoromethyl)-2-fluorobenzonitrile (CAS: 934175-58-3) is subject to regulat...

934175-58-35-(Difluoromethyl)-2...
Compound Q&A

How is Methyl 3-acetamido-2-thiophenecarboxylate (CAS: 22288-79-5) typically synthesized?

Methyl 3-acetamido-2-thiophenecarboxylate can be synthesized by the reaction of ...

22288-79-5Methyl 3-acetamido-2...
Compound Q&A

What is 4-Isoquinolinecarbonitrile (CAS: 34846-65-6)?

4-Isoquinolinecarbonitrile is a chemical compound with the CAS number 34846-65-6...

34846-65-64-Isoquinolinecarbon...
Compound Q&A

How should Methyl 1H-1,2,3-triazole-4-carboxylate (CAS: 877309-59-6) be stored?

Store Methyl 1H-1,2,3-triazole-4-carboxylate (CAS: 877309-59-6) in a cool, dry p...

877309-59-6Methyl 1H-1,2,3-tria...
Compound Q&A

What regulatory guidelines apply to 6-Bromo[1,3]thiazolo[5,4-b]pyridin-2-amine (CAS: 1160791-13-8)?

6-Bromo[1,3]thiazolo[5,4-b]pyridin-2-amine (CAS: 1160791-13-8) is subject to the...

1160791-13-86-Bromo[1,3]thiazolo...
Compound Q&A

Is (2S,3S)-2-Ammonio-3-(3,4-dihydroxyphenyl)-3-hydroxypropanoate (CAS: 23651-95-8) safe?

(2S,3S)-2-Ammonio-3-(3,4-dihydroxyphenyl)-3-hydroxypropanoate (CAS: 23651-95-8) ...

23651-95-8(2S,3S)-2-Ammonio-3-...
Compound Q&A

What are the physical and chemical properties of 7-bromo-3-methyl-3,4-dihydroquinazolin-4-one (CAS: 1293987-84-4)?

7-Bromo-3-methyl-3,4-dihydroquinazolin-4-one is a solid with a crystalline form....

1293987-84-47-bromo-3-methyl-3,4...

Source Journal

Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
Self-citation Rate: 10.3%
Articles per Year: 3036

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

Recommended Suppliers

Disclaimer
This page provides academic journal information for reference and research purposes only. We are not affiliated with any journal publishers and do not handle publication submissions. For publication-related inquiries, please contact the respective journal publishers directly.
If you notice any inaccuracies in the information displayed, please contact us at support@chemtradehub.com. We will promptly review and address your concerns.