Easy and accurate computation of energy barriers for carbocation solvation: an expeditious tool to face carbocation chemistry

Literature Information

Publication Date 2023-10-25
DOI 10.1039/D3CP03544A
Impact Factor 3.676
Authors

Antonio G. Martínez, Hans-Ulrich Siehl, Santiago de la Moya


View Original

Abstract

An expeditious procedure for the challenging computation of the free energy barriers (ΔG≠) for the solvation of carbocations is presented. This procedure is based on Marcus Theory (MT) and the popular B3LYP/6-31G(d)//PCM method, and it allows the easy, accurate and inexpensive prediction of these barriers for carbocations of very different stability. This method was validated by the fair mean absolute error (ca. 1.5 kcal mol−1) achieved in the prediction of 19 known experimental barriers covering a range of ca. 50 kcal mol−1. Interestingly, the new procedure also uses an original method for the calculation of the required inner reorganization energy (Λi) and free energy of reaction (ΔG). This procedure should pave the way to face computationally the pivotal issue of carbocation chemistry and could be easily extended to any bimolecular organic reaction.

Related Literature

Spring-like motion caused large anisotropic thermal expansion in nonporous M(eim)2 (M = Zn, Cd)

Zhanning Liu, Chenxi Liu, Qiang Li, Jun Chen, Xianran Xing

2017-07-11 Communication

DOI: 10.1039/C7CP03937A

Effect of the solvation state of electron in dissociative electron attachment reaction in aqueous solutions

Furong Wang, Pierre Archirel, Yusa Muroya, Shinichi Yamashita, Pascal Pernot, Chengying Yin, Abdel Karim El Omar, Uli Schmidhammer, Jean-Marie Teuler, Mehran Mostafavi

2017-08-11 Paper

DOI: 10.1039/C7CP03997B

A new insight into the thermodynamical criterion for the preparation of semiconductor and metal nanocrystals using a polymerized complexing method

Pingyun Li, Qingqing Wang, Guodong Deng, Xiaode Guo, Wei Jiang, Hongying Liu, Fengsheng Li

2017-08-15 Paper

DOI: 10.1039/C7CP04097K

The oxidation kinetics of thin nickel films between 250 and 500 °C

Y. Unutulmazsoy, R. Merkle, D. Fischer, J. Mannhart, J. Maier

2017-03-17 Paper

DOI: 10.1039/C7CP00476A

Potential color tunable Sr3LaNa(PO4)3F:Eu2+/Tb3+/Mn2+ phosphor induced by Eu2+ → Tb3+ and Tb3+ → Mn2+ energy transfer for WLEDs

Mengmeng Jiao, Chuanlu Yang, Yalin Li, Dongxu Wang, Hongpeng You

2017-08-21 Paper

DOI: 10.1039/C7CP04691J

New complete assignment of X-ray powder diffraction patterns in graphitic carbon nitride using discrete Fourier transform and direct experimental evidence

Bo-wen Sun, Hong-yu Yu, Yong-jing Yang, Hui-jun Li, Cheng-yu Zhai, Dong-Jin Qian, Meng Chen

2017-09-01 Paper

DOI: 10.1039/C7CP05242A

Validation of density functionals for pancake-bonded π-dimers; dispersion is not enough

Zhongyu Mou, Yong-Hui Tian, Miklos Kertesz

2017-08-09 Paper

DOI: 10.1039/C7CP04637E

Facet dependent pairwise addition of hydrogen over Pd nanocrystal catalysts revealed via NMR using para-hydrogen-induced polarization

Weiyu Wang, Jun Xu, Yanxi Zhao, Guodong Qi, Qiang Wang, Chao Wang, Jinlin Li, Feng Deng

2017-01-19 Communication

DOI: 10.1039/C7CP00352H

Quantitative prediction and interpretation of spin energy gaps in polyradicals: the virtual magnetic balance

Vincenzo Barone, Alessandro Ferretti, Giacomo Prampolini

2017-02-27 Paper

DOI: 10.1039/C7CP00186J

Back cover

Cover

DOI: 10.1039/C7CP90208E

You might also like

Compound Q&A

How should 2-Methylbenzene-1,4-diamine dihydrochloride (CAS: 615-45-2) be stored?

2-Methylbenzene-1,4-diamine dihydrochloride (CAS: 615-45-2) should be stored in ...

615-45-22-Methylbenzene-1,4-...
Compound Q&A

Is (1S,4S)-2,5-Diazabicyclo[2.2.1]heptane dihydrobromide (CAS: 132747-20-7) safe?

(1S,4S)-2,5-Diazabicyclo[2.2.1]heptane dihydrobromide is generally considered sa...

132747-20-7(1S,4S)-2,5-Diazabic...
Compound Q&A

What industries use (6-Chloropyridazin-3-YL)methanamine (CAS: 871826-15-2)?

(6-Chloropyridazin-3-YL)methanamine finds applications in the pharmaceutical ind...

871826-15-2(6-Chloropyridazin-3...
Compound Q&A

What are the main uses of 2-Fluoro-3-methylphenol (CAS: 77772-72-6)?

2-Fluoro-3-methylphenol is primarily used in the synthesis of pharmaceuticals, p...

77772-72-62-Fluoro-3-methylphe...
Compound Q&A

What precautions should be taken when handling 3-Methoxy-4-nitrobenzonitrile (CAS: 177476-75-4)?

When handling 3-Methoxy-4-nitrobenzonitrile, it is important to wear appropriate...

177476-75-43-Methoxy-4-nitroben...
Compound Q&A

What precautions should be taken when handling 1,3-Oxazolo[4,5-b]pyridine-2(3H)-thione (CAS: 211949-57-4)?

When handling 1,3-Oxazolo[4,5-b]pyridine-2(3H)-thione (CAS: 211949-57-4), it is ...

211949-57-4[1,3]Oxazolo[4,5-b]p...
Compound Q&A

What regulatory guidelines apply to 4-Ethynylbenzamide (CAS: 90347-86-7)?

4-Ethynylbenzamide (CAS: 90347-86-7) falls under various regulatory guidelines i...

90347-86-74-Ethynylbenzamide
Compound Q&A

What are the main uses of 3-(2-Ethylphenyl)-2-thioxo-4-imidazolidinone (CAS: 186822-57-1)?

3-(2-Ethylphenyl)-2-thioxo-4-imidazolidinone is primarily used as an intermediat...

186822-57-13-(2-Ethylphenyl)-2-...
Compound Q&A

What is (2-Fluoro-6-methoxyphenyl)acetic acid (CAS: 500912-19-6)?

(2-Fluoro-6-methoxyphenyl)acetic acid, also known as 4-fluoro-3-methoxybenzoic a...

500912-19-6(2-Fluoro-6-methoxyp...
Compound Q&A

What is the market or research trend for 2-[4-(Hydroxymethyl)phenoxy]ethanol (CAS: 102196-18-9)?

Market trends for 2-[4-(Hydroxymethyl)phenoxy]ethanol (CAS: 102196-18-9) indicat...

102196-18-92-[4-(Hydroxymethyl)...

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 Compounds

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.