Development of methods for the description of complex-forming bimolecular reactions  Page description

Help  Print 
Back »

 

Details of project

 
Identifier
108966
Type K
Principal investigator Lendvay, György
Title in Hungarian Komplexképződéssel járó elemi reakciók kinetikájának leírására alkalmas elméleti módszerek fejlesztése
Title in English Development of methods for the description of complex-forming bimolecular reactions
Keywords in Hungarian elemi kémiai reakció, reakciókinetika, reakciódinamika, reakciósebességi elmélet
Keywords in English elementray chemical reaction, reaction kinetocs, reaction dynamics, reaction rate theory
Discipline
Physical Chemistry and Theoretical Chemistry (Council of Physical Sciences)100 %
Ortelius classification: Physical chemistry
Panel Chemistry 1
Department or equivalent Institute of Materials and Environmental Chemistry (Research Center of Natural Sciences, Hungarian Academy of Sciences)
Participants Bencsura, Ákos
Mayer, István
Nagy, Tibor
Nagy, Tibor
Rozgonyi, Tamás
Szabó, Péter
Vikár, Anna
Starting date 2013-09-01
Closing date 2018-08-31
Funding (in million HUF) 26.988
FTE (full time equivalent) 8.79
state running project





 

Final report

 
Results in Hungarian
A projektben elméleti úton elemi kémiai reakciók tulajdonságait tanulmányoztuk, és a leírásukra alkalmas módszereket fejlesztettünk, a következő eredményekkel. - Megmutattuk, hogy a kváziklasszikus trajektória módszerben rutinszerűen használt szemiklasszikus kezdetiérték számító módszer félrevezető jelenségeket okozhat, és helyette új, a sokatomos molekulák kezelésére alkalmas, az anharmonicitás adiabatikus bekapcsolásán alapuló módszert fejlesztettünk ki. Ennek alkalmazásával megmutattuk, hogy a redukált-dimenziós kvantummechanikai módszerek kvalitatíve helyesen írják le egyes reakciótípusok viselkedését, de kvantitatív pontosságuk nem garantált. - Meghatároztuk több elemi reakció eddig nem ismert , illetve nem minden hőmérséklettartományban ismert nagyságú sebességi együtthatóját (H + (1)O2, CH3 + HBr, OH + HBr, NCN disszociáció, CH3CHCHCH2 + O2). - Megállapítottuk, hogy az O + O2 , a H + O2, CH3 + HBr és OH + HBr komplexképződéssel járó bimolekulás reakciókban a komplex nem statisztikusan viselkedik, és ezzel a leírásukra használt átmenetiállapot-elmélet egyik alapfeltevése nem teljesül. - Kísérleti vizsgálatok kiegészítésére illetve eredményeik értelmezésére kvantumkémiai és reakciókinetikai számításokat végeztünk katalizátornak alkalmas átmenetifém-komplexek képződésének felderítése illetve tulajdonságaik leírása céljából.
Results in English
In this project properties of elementary chemical reactions have been studied using theoretical methods, and new techniques for their description have been developed. The main results are: - We have shown that the normal mode sampling method, routinely used in quasiclassical trajectory calculations may produce unphysical phenomena such as oscillatory reaction probabilities. A method based on adiabatic switching of the anharmonicities has been developed, which allows one to avoid these discrepancies. We demonstrated that the reduced-dimensional quantum dynamical models are qualitatively correct, but their quantitative accuracy is not guaranteed. - Rate coefficients that were unknown or known only in limited temperature ranges have been determined for several reactions (H + 1O2, CH3 + HBr, OH + HBr, CH3CHCHCH2 + O2, thermal dissociation of NCN). - The complexes formed in the complex-forming O + O2, H + O2, CH3 + HBr and OH + HBr reactions have been shown not to behave statistically, because of which one of the basic assumptions of transition state theory (which is routinely used for the description of such reactions) is not fulfilled. - Model calculations using theories of electronic structure and reaction kinetics have been performed on transition metal complexes synthesized by our experimentalist collaborators, to determine the conditions and kinetics of their formation as well as their structure and properties.
Full text https://www.otka-palyazat.hu/download.php?type=zarobeszamolo&projektid=108966
Decision
Yes





 

List of publications

 
Cs. Fehér, M. Papp, Á. Gömöry, L. Nagy, J. Wouters, G. Lendvay, R. Skoda-Földes: Synthesis of 2-Ureido-4-ferrocenyl Pyrimidine Guests. Investigation of Complementary Molecular Recognition of 2,6-Diaminopyridine, Organometallics 36, 4023–4032, 2016
Kovács E, Sághy P, Turczel G, Tóth I, Lendvay G, Domján A, Anastas PT, Tuba R: Metathesis o renewable polyene feedstocks - Indirect evidences of the formation of catalytically active ruthenium allylidene species, J ORGANOMET CHEM 847: 213-217, 2017
Nagy Tibor, Lendvay György: Adiabatic Switching Extended to Prepare Semiclassically Quantized Rotational-Vibrational Initial States for Quasiclassical Trajectory Calculations, J PHYS CHEM LETT 8: 4621-4626, 2017
Tajti A, Lendvay G, Szalay PG: Dimol Emission of Oxygen Made Possible by Repulsive Interaction, J PHYS CHEM LETT 8: (14) 3356-3361, 2017
Tajti A, Lendvay G, Szalay PG: Dimol Emission of Oxygen Made Possible by Repulsive Interaction, J PHYS CHEM LETT 8: (14) 3356-3361, 2017
Kovács E, Sághy P, Turczel G, Tóth I, Lendvay G, Domján A, Anastas PT, Tuba R: Metathesis o renewable polyene feedstocks - Indirect evidences of the formation of catalytically active ruthenium allylidene species, J ORGANOMET CHEM 847: 213-217, 2017
Nagy Tibor, Lendvay György: Adiabatic Switching Extended to Prepare Semiclassically Quantized Rotational-Vibrational Initial States for Quasiclassical Trajectory Calculations, J PHYS CHEM LETT 8: 4621-4626, 2017
Annalise L. Van Wyngarden, Kathleen A. Mar, Jim Quach, Anh P. Q. Nguyen, Aaron A. Wiegel, Shi-Ying Lin, Gyorgy Lendvay, Hua Guo, Jim J. Lin, Yuan T. Lee, and Kristie A. Boering: The non-statistical dynamics of the 18O + 32O2 isotope exchange reaction at two energies, J. Chem. Phys. 141, 064311 (2014) pp 1-11, 2014
Busch Anna, González-García Núria, Lendvay György, Olzmann Matthias: Thermal Decomposition of NCN: Shock-Tube Study, Quantum Chemical Calculations, and Master-Equation Modeling, J PHYS CHEM A 119: (28) 7838-7846, 2015
Szabó Péter, Lendvay György: A Quasiclassical Trajectory Study of the Reaction of H Atoms with O2(1Δg), J PHYS CHEM A 119: (28) 7180-7189, 2015
Csaszar Z, Farkas G, Benyei A, Lendvay G, Toth I, Bakos J: Stereoselective coordination: a six-membered P,N-chelate tailored for asymmetric allylic alkylation., DALTON T 44: (37) 16352-16360, 2015
Szabó Péter, Lendvay György: Dynamics of Complex-Forming Bimolecular Reactions: A Comparative Theoretical Study of the Reactions of H Atoms with O2(3Σg–) and O2(1Δg), J PHYS CHEM A 119: (50) 12485-12497, 2015
Tibor Nagy, Anna Vikár , György Lendvay: Oscillatory reaction cross sections caused by normal mode sampling in quasiclassical trajectory calculations, J CHEM PHYS 144: (1), 2016
Anna Vikár, Tibor Nagy, György Lendvay: Testing the Palma-Clary Reduced Dimensionality Model Using Classical Mechanics on the CH4 + H -> CH3 + H2 Reaction, J PHYS CHEM A 120: (27) 5083-5093, 2016
Sridhar A Lahankar, Jianming Zhang, Timothy K Minton, Hua Guo, Lendvay Gy: Dynamics of the O-Atom Exchange Reaction 16O(3P) + 18O18O(3Σ-g) -> 6O18O(3Σ-g) + 18O(3P) at Hyperthermal Energies, J PHYS CHEM A 120: 5348-5359, 2016
Annalise L. Van Wyngarden, Kathleen A. Mar, Jim Quach, Anh P. Q. Nguyen, Aaron A. Wiegel, Shi-Ying Lin, Gyorgy Lendvay, Hua Guo, Jim J. Lin, Yuan T. Lee, and Kristie A. Boering: The non-statistical dynamics of the 18O + 32O2 isotope exchange reaction at two energies, J. Chem. Phys. 141, 064311 (2014) pp 1-11, 2014
Busch Anna, González-García Núria, Lendvay György, Olzmann Matthias: Thermal Decomposition of NCN: Shock-Tube Study, Quantum Chemical Calculations, and Master-Equation Modeling, J PHYS CHEM A 2015: , 2015
Csaszar Z, Farkas G, Benyei A, Lendvay G, Toth I, Bakos J: Stereoselective coordination: a six-membered P,N-chelate tailored for asymmetric allylic alkylation., DALTON T 44: (37) 16352-16360, 2015
Szabó Péter, Lendvay György: A Quasiclassical Trajectory Study of the Reaction of H Atoms with O2(1Δg), J PHYS CHEM A 2015: , 2015
Anna Vikár, Tibor Nagy, György Lendvay: Testing the Palma-Clary Reduced Dimensionality Model Using Classical Mechanics on the CH4 + H -> CH3 + H2 Reaction, J PHYS CHEM A 120: (27) 5083-5093, 2016
Sridhar A Lahankar, Jianming Zhang, Timothy K Minton, Hua Guo, Lendvay Gy: Dynamics of the O-Atom Exchange Reaction 16O(3P) + 18O18O(3Σ-g) -> 6O18O(3Σ-g) + 18O(3P) at Hyperthermal Energies, J PHYS CHEM A 120: 5348-5359, 2016
Tibor Nagy, Anna Vikár , György Lendvay: Oscillatory reaction cross sections caused by normal mode sampling in quasiclassical trajectory calculations, J CHEM PHYS 144: (1) , 2016
Busch Anna, González-García Núria, Lendvay György, Olzmann Matthias: Thermal Decomposition of NCN: Shock-Tube Study, Quantum Chemical Calculations, and Master-Equation Modeling, J PHYS CHEM A 119: (28) 7838-7846, 2015
Szabó Péter, Lendvay György: A Quasiclassical Trajectory Study of the Reaction of H Atoms with O2(1Δg), J PHYS CHEM A 119: (28) 7180-7189, 2015
Szabó Péter, Lendvay György: Dynamics of Complex-Forming Bimolecular Reactions: A Comparative Theoretical Study of the Reactions of H Atoms with O2(3Σg–) and O2(1Δg), J PHYS CHEM A 119: (50) 12485-12497, 2015
Farkas G, Császár Z, Stágel K, Nemes E, Balogh S, Tóth I, Bényei A, Lendvay G, Bakos J: Efficient stereochemical communication in phosphine-amine palladium-complexes: exploration of N-substituent effects in coordination chemistry and catalysis, J ORGANOMET CHEM 846: pp. 129-140., 2017
Góger Szabolcs, Szabó Péter, Czako G, Lendvay G: Flame inhibition chemistry: Rate coefficients of the reactions of HBr with CH3 and OH radicals at high temperatures determined by quasiclassical trajectory calculations, ENERG FUEL &:, 2018
L Szi-Ferenc, Zs Császár, Gy Lendvay, A Bényei, Sz Balogh, B Nánási, G Farkas, J Bakos: Synthesis of zwitterionic phosphapalladacycles: unusual reactivity pattern of six-membered P,N-chelates, ORGANOMETALLICS 37: (14) pp. 2203-2206., 2018
Pekkanen TT, Timonen RS, Lendvay G, Rissanen MP, Eskola AJ: Kinetics and Thermochemistry of the Reaction of 3-Methylpropargyl Radical with Molecular Oxygen, P COMBUST INST &:, 2018
Tibor Nagy, Anna Vikár, György Lendvay: A General Formulation of the Quasiclassical Trajectory Method for Reduced-Dimensionality Reaction Dynamics Calculations, PHYS CHEM CHEM PHYS 20: pp. 13224-13240., 2018
Császár Zs, Stágel K, Balogh Sz, Bényei A, Lendvay Gy, Farkas G, Bakos J: Steric effects enforce double stereoselective N-coordination in twelvemembered binuclear palladium(II)-complexes containing chiral bridging aminoalkyl-phosphine ligands, J ORGANOMET CHEM 855: pp. 59-62., 2018





 

Events of the project

 
2017-12-15 14:51:47
Résztvevők változása
2016-08-28 19:46:16
Résztvevők változása
2014-10-06 14:47:18
Résztvevők változása




Back »