Understanding and controlling the atomic-level dynamics of chemical reactions: From fundamental processes to small biosystems  Page description

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Details of project

  
Identifier
125317
Type K
Principal investigator Czakó, Gábor
Title in Hungarian Kémiai reakciók dinamikájának atomi szintű vizsgálata és szabályozása: alapvető folyamatoktól a kis biorendszerek tanulmányozásáig
Title in English Understanding and controlling the atomic-level dynamics of chemical reactions: From fundamental processes to small biosystems
Keywords in Hungarian reakciódinamika, ab initio, metán reakciói, SN2 reakciók, aminosavak
Keywords in English reaction dynamics, ab initio, reactions of methane, SN2 reactions, amino acids
Discipline
Physical Chemistry and Theoretical Chemistry (Council of Physical Sciences)100 %
Ortelius classification: Physical chemistry
Panel Chemistry 1
Department or equivalent Department of Physical Chemistry and Materials Science (University of Szeged)
Participants Olasz, Balázs
Papp, Dóra
Yin, Cangtao
Starting date 2017-09-01
Closing date 2023-11-30
Funding (in million HUF) 41.361
FTE (full time equivalent) 7.30
state running project





 

Final report

  
Results in Hungarian
Új eszközöket (Robosurfer és ManyHF) fejlesztettünk ki kémiai reakciók atomi-szintű dinamikájának és mechanizmusainak automatikus modellezéséhez. A Robosurfer programcsomag felhasználásával analitikus ab initio potenciálisenergia-felületeket fejlesztettünk számos rendszerre, mint például a F, Cl, OH, HBr és HI reakciói C2H6 vagy C2H5 molekulákkal, valamint különböző ion-molekula reakciókra. Ezeken a felületeken a dinamika szimulációink újszerű reakcióutakat tártak fel, úgymint a multi-inverzió és az oxidion szubsztitúció, megfejtették a helyettesítéses (SN2) és eliminációs (E2) reakciók versengését, betekintést engedtek a rezgési és forgási mód-specificitásba és minden korábbinál pontosabb egyezést mutattak a kísérletekkel. Továbbá szintén tanulmányoztuk molekuláris komplexek dinamikáját, valamint aminosavak dehidrogénezését és protonálódását.
Results in English
We have developed new tools (Robosurfer and ManyHF) for automatically modelling the atomic-level dynamics and mechanisms of chemical reactions. Using the Robosurfer program package, we have constructed analytical ab initio potential energy surfaces (PESs) for several systems like, for example, reactions of F, Cl, OH, HBr, and HI with C2H6 or C2H5 as well as for various ion-molecule reactions. Our dynamics simulations on these surfaces have revealed novel reaction pathways such as multi-inversion and oxide-ion substitution, disentangled the competition between substitution (SN2) and elimination (E2), uncovered vibrational and rotational mode specificity, and provided unprecedented agreement with experiments. Furthermore, we have also studied the dynamics of molecular complexes as well as the dehydrogenation and protonation of amino acids.
Full text https://www.otka-palyazat.hu/download.php?type=zarobeszamolo&projektid=125317
Decision
Yes





 

List of publications

  
I. Szabó and G. Czakó: Dynamics and novel mechanisms of SN2 reactions on ab initio analytical potential energy surfaces, J. Phys. Chem. A 121, 9005, 2017
L. Krotos and G. Czakó: Does the Cl + CH4 --> H + CH3Cl reaction proceed via Walden inversion?, J. Phys. Chem. A 121, 9415, 2017
B. Hajdu and G. Czakó: Benchmark ab initio characterization of the complex potential energy surfaces of the X- + NH2Y [X,Y = F, Cl, Br, I] reactions, J. Phys. Chem. A 122, 1886, 2018
T. Győri, B. Olasz, G. Paragi, and G. Czakó: Effects of the level of electronic structure theory on the dynamics of the F- + CH3I reaction, J. Phys. Chem. A 122, 3353, 2018
S. Góger, P. Szabó, G. Czakó, and G. Lendvay: Flame inhibition chemistry: rate coefficients of the reactions of HBr with CH3 and OH radicals at high temperatures determined by quasiclassical trajectory calculations, Energy Fuels DOI: 10.1021/acs.energyfuels.8b00989, 2018
M. Stei, E. Carrascosa, A. Dörfler, J. Meyer, B. Olasz, G. Czakó, A. Li, H. Guo, and R. Wester: Stretching vibration is spectator in nucleophilic substitution, Sci. Adv. 4, eaas9544, 2018
D. A. Tasi, Z. Fábián, and G. Czakó: Benchmark ab initio characterization of the inversion and retention pathways of the OH- + CH3Y [Y = F, Cl, Br, I] SN2 reactions, J. Phys. Chem. A 122, 5773, 2018
B. Hajdu and G. Czakó: Benchmark ab initio characterization of the complex potential energy surfaces of the X- + NH2Y [X,Y = F, Cl, Br, I] reactions, J. Phys. Chem. A 122, 1886, 2018
T. Győri, B. Olasz, G. Paragi, and G. Czakó: Effects of the level of electronic structure theory on the dynamics of the F- + CH3I reaction, J. Phys. Chem. A 122, 3353, 2018
S. Góger, P. Szabó, G. Czakó, and G. Lendvay: Flame inhibition chemistry: rate coefficients of the reactions of HBr with CH3 and OH radicals at high temperatures determined by quasiclassical trajectory calculations, Energy Fuels 32, 10100, 2018
M. Stei, E. Carrascosa, A. Dörfler, J. Meyer, B. Olasz, G. Czakó, A. Li, H. Guo, and R. Wester: Stretching vibration is spectator in nucleophilic substitution, Sci. Adv. 4, eaas9544, 2018
D. A. Tasi, Z. Fábián, and G. Czakó: Benchmark ab initio characterization of the inversion and retention pathways of the OH- + CH3Y [Y = F, Cl, Br, I] SN2 reactions, J. Phys. Chem. A 122, 5773, 2018
B. Olasz and G. Czakó: Mode-specific quasiclassical dynamics of the F- + CH3I SN2 and proton-transfer reactions, J. Phys. Chem. A 122, 8143, 2018
D. Papp, B. Gruber, and G. Czakó: Detailed benchmark ab initio mapping of the potential energy surfaces of the X + C2H6 [X = F, Cl, Br, I] reactions, Phys. Chem. Chem. Phys. 21, 396, 2019
B. Bastian, E. Carrascosa, A. Kaiser, J. Meyer, T. Michaelsen, G. Czakó, W. L. Hase, and R. Wester: Dynamics of proton transfer from ArH+ to CO, Int. J. Mass Spectrom. 438, 175, 2019
B. Olasz and G. Czakó: High-level-optimized stationary points for the F-(H2O) + CH3I system: Proposing a new water-induced double-inversion pathway, J. Phys. Chem. A 123, 454, 2019
B. Olasz and G. Czakó: Uncovering the role of the stationary points in the dynamics of the F- + CH3I reaction, Phys. Chem. Chem. Phys. 21, 1578, 2019
D. A. Tasi, Z. Fábián, and G. Czakó: Rethinking the X- + CH3Y [X = OH, SH, CN, NH2, PH2; Y = F, Cl, Br, I] SN2 reactions, Phys. Chem. Chem. Phys. 21, 7924, 2019
G. Czakó: Dynamics and mechanisms of fundamental chemical reactions, Magy. Kém. Foly. 125, 100, 2019
G. Czakó, T. Győri, B. Olasz, D. Papp, I. Szabó, V. Tajti, and D. A. Tasi: Benchmark ab initio and dynamical characterization of the stationary points of reactive atom + alkane and SN2 potential energy surfaces, Phys. Chem. Chem. Phys. 22, 4298, 2020
T. Győri and G. Czakó: Automating the development of high-dimensional reactive potential energy surfaces with the ROBOSURFER program system, J. Chem. Theory Comput. 16, 51, 2020
G. Avila, D. Papp, G. Czakó, and E. Mátyus: Exact quantum dynamics background of dispersion interactions: case study for CH4.Ar in full (12) dimensions, Phys. Chem. Chem. Phys. 22, 2792, 2020
D. A. Tasi, T. Győri, and G. Czakó: On the development of a gold-standard potential energy surface for the OH- + CH3I reaction, Phys. Chem. Chem. Phys. 22, 3775, 2020
D. Papp, V. Tajti, T. Győri, and G. Czakó: Theory finally agrees with experiment for the dynamics of the Cl + C2H6 reaction, J. Phys. Chem. Lett. 11, 4762, 2020
E. M. Orján, A. B. Nacsa, and G. Czakó: Conformers of dehydrogenated glycine isomers, J. Comput. Chem. 41, 2001, 2020
B. Gruber and G. Czakó: Benchmark ab initio characterization of the abstraction and substitution pathways of the OH + CH4/C2H6 reactions, Phys. Chem. Chem. Phys. 22, 14560, 2020
P. Papp, V. Tajti, and G. Czakó: Numerical separation of the front-side attack and double-inversion retention pathways of SN2 reactions, Chem. Phys. Lett. 755, 137780, 2020
D. Papp and G. Czakó: Full-dimensional MRCI-F12 potential energy surface and dynamics of the F(2P3/2) + C2H6 --> HF + C2H5 reaction, J. Chem. Phys. 153, 064305, 2020
P. Papp and G. Czakó: Rotational mode specificity in the F− + CH3I(v=0, JK) SN2 and proton-transfer reactions, J. Phys. Chem. A 124, 8943, 2020
G. Czakó, T. Győri, D. Papp, V. Tajti, and D. A. Tasi: First-principles reaction dynamics beyond six-atom systems, J. Phys. Chem. A 125, 2385, 2021
D. Papp and G. Czakó: Facilitated inversion complicates the stereodynamics of an SN2 reaction at nitrogen center, Chem. Sci. 12, 5410, 2021
A. B. Nacsa and G. Czakó: Benchmark ab initio proton affinity of glycine, Phys. Chem. Chem. Phys. 23, 9663, 2021
T. Szűcs and G. Czakó: Benchmark ab initio stationary-point characterization of the complex potential energy surface of the multi-channel Cl + CH3NH2 reaction, Phys. Chem. Chem. Phys. 23, 10347, 2021
D. A. Tasi, C. Tokaji, and G. Czakó: A benchmark ab initio study of the complex potential energy surfaces of the OH− + CH3CH2Y [Y = F, Cl, Br, I] reactions, Phys. Chem. Chem. Phys. 23, 13526, 2021
J. Meyer, V. Tajti, E. Carrascosa, T. Győri, M. Stei, T. Michaelsen, B. Bastian, G. Czakó, and R. Wester: Atomistic dynamics of elimination and nucleophilic substitution disentangled for the F− + CH3CH2Cl reaction, Nat. Chem. DOI: 10.1038/s41557-021-00753-8, 2021
D. Papp, J. Li, H. Guo, and G. Czakó: Vibrational mode-specificity in the dynamics of the Cl + C2H6 → HCl + C2H5 reaction, J. Chem. Phys. 155, 114303, 2021
V. Tajti, T. Győri, and G. Czakó: Detailed quasiclassical dynamics of the F− + CH3Br reaction on an ab initio analytical potential energy surface, J. Chem. Phys. 155, 124301, 2021
D. Papp and G. Czakó: Vibrational mode-specific dynamics of the F(2P3/2) + C2H6 → HF + C2H5 reaction, J. Chem. Phys. accepted, 2021
A. Á. Dékány and G. Czakó: Benchmark ab initio proton affinity and gas-phase basicity of α-alanine based on coupled-cluster theory and statistical mechanics, J. Comput. Chem. accepted, 2021
G. Czakó, T. Győri, D. Papp, V. Tajti, and D. A. Tasi: First-principles reaction dynamics beyond six-atom systems, J. Phys. Chem. A 125, 2385, 2021
D. Papp and G. Czakó: Facilitated inversion complicates the stereodynamics of an SN2 reaction at nitrogen center, Chem. Sci. 12, 5410, 2021
A. B. Nacsa and G. Czakó: Benchmark ab initio proton affinity of glycine, Phys. Chem. Chem. Phys. 23, 9663, 2021
T. Szűcs and G. Czakó: Benchmark ab initio stationary-point characterization of the complex potential energy surface of the multi-channel Cl + CH3NH2 reaction, Phys. Chem. Chem. Phys. 23, 10347, 2021
D. A. Tasi, C. Tokaji, and G. Czakó: A benchmark ab initio study of the complex potential energy surfaces of the OH− + CH3CH2Y [Y = F, Cl, Br, I] reactions, Phys. Chem. Chem. Phys. 23, 13526, 2021
J. Meyer, V. Tajti, E. Carrascosa, T. Győri, M. Stei, T. Michaelsen, B. Bastian, G. Czakó, and R. Wester: Atomistic dynamics of elimination and nucleophilic substitution disentangled for the F− + CH3CH2Cl reaction, Nat. Chem. 13, 977, 2021
D. Papp, J. Li, H. Guo, and G. Czakó: Vibrational mode-specificity in the dynamics of the Cl + C2H6 → HCl + C2H5 reaction, J. Chem. Phys. 155, 114303, 2021
V. Tajti, T. Győri, and G. Czakó: Detailed quasiclassical dynamics of the F− + CH3Br reaction on an ab initio analytical potential energy surface, J. Chem. Phys. 155, 124301, 2021
D. Papp and G. Czakó: Vibrational mode-specific dynamics of the F(2P3/2) + C2H6 → HF + C2H5 reaction, J. Chem. Phys. 155, 154302, 2021
A. Á. Dékány and G. Czakó: Benchmark ab initio proton affinity and gas-phase basicity of α-alanine based on coupled-cluster theory and statistical mechanics, J. Comput. Chem. 43, 19, 2022
D. A. Tasi and G. Czakó: Uncovering an oxide ion substitution for the OH− + CH3F reaction, Chem. Sci. 12, 14369, 2021
A. Á. Dékány, G. Z. Kovács, and G. Czakó: High-level systematic ab initio comparison of carbon- and silicon-centered SN2 reactions, J. Phys. Chem. A 125, 9645, 2021
Z. Kerekes, D. A. Tasi, and G. Czakó: SN2 reactions with an ambident nucleophile: A benchmark ab initio study of the CN− + CH3Y [Y = F, Cl, Br, and I] systems, J. Phys. Chem. A 126, 889, 2022
T. Győri and G. Czakó: ManyHF: A pragmatic automated method of finding lower-energy Hartree−Fock solutions for potential energy surface development, J. Chem. Phys. 156, 071101, 2022
V. Tajti and G. Czakó: Vibrational mode-specific dynamics of the F− + CH3CH2Cl multi-channel reaction, Phys. Chem. Chem. Phys. 24, 8166, 2022
D. Papp and G. Czakó: Rotational mode-specificity in the Cl + C2H6 → HCl + C2H5 reaction, J. Phys. Chem. A 126, 2551, 2022
P. Tóth, T. Szűcs, and G. Czakó: Benchmark ab initio characterization of the abstraction and substitution pathways of the Cl + CH3CN reaction, J. Phys. Chem. A 126, 2802, 2022
D. A. Tasi and G. Czakó: Unconventional SN2 retention pathways induced by complex formation: High-level dynamics investigation of the NH2− + CH3I polyatomic reaction, J. Chem. Phys. 156, 184306, 2022
B. Gruber, V. Tajti, and G. Czakó: Full-dimensional automated potential energy surface development and dynamics for the OH + C2H6 reaction, J. Chem. Phys. 157, 074307, 2022
T. Szűcs and G. Czakó: Benchmark ab initio potential energy surface mapping of the F + CH3NH2 reaction, Phys. Chem. Chem. Phys. 24, 20249, 2022
D. Papp, V. Tajti, G. Avila, E. Mátyus, and G. Czakó: CH4·F− revisited: full-dimensional ab initio potential energy surface and variational vibrational states, Mol. Phys. DOI: 10.1080/00268976.2022.2113565, 2022
C. Yin, V. Tajti, and G. Czakó: Full-dimensional potential energy surface development and dynamics for the HBr + C2H5 → Br(2P3/2) + C2H6 reaction, Phys. Chem. Chem. Phys. DOI: 10.1039/D2CP03580D, 2022
A. Á. Dékány and G. Czakó: Benchmark ab initio proton affinity and gas-phase basicity of α-alanine based on coupled-cluster theory and statistical mechanics, J. Comput. Chem. 43, 19, 2022
Z. Kerekes, D. A. Tasi, and G. Czakó: SN2 reactions with an ambident nucleophile: A benchmark ab initio study of the CN− + CH3Y [Y = F, Cl, Br, and I] systems, J. Phys. Chem. A 126, 889, 2022
T. Győri and G. Czakó: ManyHF: A pragmatic automated method of finding lower-energy Hartree−Fock solutions for potential energy surface development, J. Chem. Phys. 156, 071101, 2022
V. Tajti and G. Czakó: Vibrational mode-specific dynamics of the F− + CH3CH2Cl multi-channel reaction, Phys. Chem. Chem. Phys. 24, 8166, 2022
D. Papp and G. Czakó: Rotational mode-specificity in the Cl + C2H6 → HCl + C2H5 reaction, J. Phys. Chem. A 126, 2551, 2022
P. Tóth, T. Szűcs, and G. Czakó: Benchmark ab initio characterization of the abstraction and substitution pathways of the Cl + CH3CN reaction, J. Phys. Chem. A 126, 2802, 2022
D. A. Tasi and G. Czakó: Unconventional SN2 retention pathways induced by complex formation: High-level dynamics investigation of the NH2− + CH3I polyatomic reaction, J. Chem. Phys. 156, 184306, 2022
B. Gruber, V. Tajti, and G. Czakó: Full-dimensional automated potential energy surface development and dynamics for the OH + C2H6 reaction, J. Chem. Phys. 157, 074307, 2022
T. Szűcs and G. Czakó: Benchmark ab initio potential energy surface mapping of the F + CH3NH2 reaction, Phys. Chem. Chem. Phys. 24, 20249, 2022
D. Papp, V. Tajti, G. Avila, E. Mátyus, and G. Czakó: CH4·F− revisited: full-dimensional ab initio potential energy surface and variational vibrational states, Mol. Phys. 121, e2113565, 2023
C. Yin, V. Tajti, and G. Czakó: Full-dimensional potential energy surface development and dynamics for the HBr + C2H5 → Br(2P3/2) + C2H6 reaction, Phys. Chem. Chem. Phys. 24, 24784, 2022
C. Yin and G. Czakó: Automated full-dimensional potential energy surface development and quasi-classical dynamics for the HI(X1Σ+) + C2H5 → I(2P3/2) + C2H6 reaction, Phys. Chem. Chem. Phys. 24, 29084, 2022
A. B. Nacsa and G. Czakó: Benchmark ab initio determination of the conformers, proton affinities, and gas-phase basicities of cysteine, J. Phys. Chem. A 126, 9667, 2022
C. Yin and G. Czakó: Theoretical vibrational mode-specific dynamics studies for the HBr + C2H5 reaction, Phys. Chem. Chem. Phys. 25, 3083, 2023
D. A. Tasi, T. Michaelsen, R. Wester, and G. Czakó: Quasi-classical trajectory study of the OH− + CH3I reaction: Theory meets experiment, Phys. Chem. Chem. Phys. 25, 4005, 2023
T. Győri and G. Czakó: A comprehensive benchmark ab initio survey of the stationary points and products of the OH· + CH3OH system, J. Chem. Phys. 158, 034301, 2023
B. Gruber and G. Czakó: High-level ab initio mapping of the multiple H-abstraction pathways of the OH + glycine reaction, Phys. Chem. Chem. Phys. 25, 5271, 2023
A. B. Nacsa, M. Kígyósi, and G. Czakó: Protonation of serine: Conformers, proton affinities and gas-phase basicities at the "gold standard" and beyond, Phys. Chem. Chem. Phys. 25, 8891, 2023
C. Yin and G. Czakó: Vibrational mode-specific quasi-classical trajectory studies for the two-channel HI + C2H5 reaction, Phys. Chem. Chem. Phys. 25, 9944, 2023
A. B. Nacsa, V. Tajti, and G. Czakó: Dynamics of the Cl− + CH3I reaction on a high-level ab initio analytical potential energy surface, J. Chem. Phys. 158, 194306, 2023
A. Á. Dékány and G. Czakó: Exploring the versatile reactivity of the F− + SiH3Cl system on a full-dimensional coupled-cluster potential energy surface, J. Chem. Phys. 158, 224303, 2023
T. Gstir, T. Michaelsen, B. A. Long, A. B. Nacsa, A. Ayasli, D. Swaraj, F. Zappa, F. Trummer, S. G. Ard, N. S. Shuman, G. Czakó, A. A. Viggiano, and R. Wester: The influence of fluorination on the dynamics of the F− + CH3CH2I reaction, Phys. Chem. Chem. Phys. 25, 18711, 2023
C. Yin and G. Czakó: Competition between the H-abstraction and the X-abstraction pathways in the HX (X = Br, I) + C2H5 reactions, Phys. Chem. Chem. Phys. 25, 20241, 2023
A. Giricz, G. Czakó, and D. Papp: Alternating stereospecificity upon central-atom change: Dynamics of the F− + PH2Cl SN2 reaction compared to its C- and N-centered analogues, Chem. Eur. J. DOI: 10.1002/chem.202302113, 2023
B. Gruber, V. Tajti, and G. Czakó: Vibrational mode-specific dynamics of the OH + C2H6 reaction, J. Phys. Chem. A 127, 7364, 2023
T. Szűcs and G. Czakó: ManyHF-based full-dimensional potential energy surface development and quasi-classical dynamics for the Cl + CH3NH2 reaction, J. Chem. Phys. DOI: 10.1063/5.0166680, 2023
C. Yin and G. Czakó: Full-dimensional automated potential energy surface development and detailed dynamics for the CH2OO + NH3 reaction, Phys. Chem. Chem. Phys. DOI: 10.1039/D3CP03469K, 2023
A. Giricz, G. Czakó, and D. Papp: Alternating stereospecificity upon central-atom change: Dynamics of the F− + PH2Cl SN2 reaction compared to its C- and N-centered analogues, Chem. Eur. J. 29, e202302113, 2023
T. Szűcs and G. Czakó: ManyHF-based full-dimensional potential energy surface development and quasi-classical dynamics for the Cl + CH3NH2 reaction, J. Chem. Phys. 159, 134306, 2023
C. Yin and G. Czakó: Full-dimensional automated potential energy surface development and detailed dynamics for the CH2OO + NH3 reaction, Phys. Chem. Chem. Phys. 25, 26917, 2023
B. Ballay, T. Szűcs, D. Papp, and G. Czakó: Phosphorus-centered ion-molecule reactions: benchmark ab initio characterization of the potential energy surfaces of the X− + PH2Y [X, Y = F, Cl, Br, I] systems, Phys. Chem. Chem. Phys. 25, 28925, 2023




 

Events of the project

  
2022-07-12 15:15:04
Résztvevők változása
2018-07-18 16:01:33
Résztvevők változása
2017-11-17 09:51:47
Résztvevők változása



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