Pressure-Driven Phase Transition Mechanisms Revealed by Quantum Chemistry: L-Serine Polymorphs | Sciact - CRIS-система Института катализа

Pressure-Driven Phase Transition Mechanisms Revealed by Quantum Chemistry: L-Serine Polymorphs Научная публикация

Журнал

PCCP: Physical Chemistry Chemical Physics
ISSN: 1463-9076 , E-ISSN: 1463-9084

Вых. Данные

Год: 2017, Том: 19, Номер: 9, Страницы: 6671-6676 Страниц : 6 DOI: 10.1039/c6cp07721h

Ключевые слова

CRYSTAL-STRUCTURE PREDICTION; TOTAL-ENERGY CALCULATIONS; WAVE BASIS-SET; KINETIC CONTROL; DIFFRACTION; GPA; BEHAVIOR

Авторы

Rychkov D.A. ^1,2 , Stare J. ³ , Boldyreva E.V. ¹

Организации

1	Institute of Solid State Chemistry and Mechanochemistry, Siberian Branch of Russian Academy of Sciences, ul. Kutateladze, 18, Novosibirsk 630128, Russian Federation
2	Novosibirsk State University, ul. Pirogova, 2, Novosibirsk 630090, Russian Federation
3	National Institute of Chemistry, 19 Hajdrihova str., SI-1000, Ljubljana, Slovenia

Информация о финансировании (2)

1	Российский научный фонд	14-13-00834
2	Slovenian Research Agency	P1-0012

The present study delivers a computational approach for the understanding of the mechanism of phase transitions between polymorphs of small organic molecules. By using state of the art periodic DFT calculations augmented with dispersion corrections and an external stress tensor together with gas-phase cluster calculations, we thoroughly explained the reversible phase transitions of three polymorphs of the model system, namely crystalline l-serine in the pressure range up to 8 GPa. This study has shown that at the macroscopic level the main driving force of the phase transitions is the decrease in the volume of the crystal unit cell, which contributes to the enthalpy difference between the two forms, but not to the difference in their internal crystal energies. At the microscopic level we suggest that hydrogen bond overstrain leads to a martensitic-like, cooperative, displacive phase transition with substantial experimental hysteresis, while no such overstrain was found for the "normal type", atom per atom, reconstructive phase transition. The predicted pressures for the phase transitions deducted by the minimum enthalpy criterion are in reasonable agreement with the observed ones. By delivering unambiguous explanations not provided by previous studies and probably not accessible to experiment, this work demonstrates the predictive and explanatory power of quantum chemistry, confirming its indispensable role in structural studies.

Rychkov D.A. , Stare J. , Boldyreva E.V.
Pressure-Driven Phase Transition Mechanisms Revealed by Quantum Chemistry: L-Serine Polymorphs

PCCP: Physical Chemistry Chemical Physics. 2017. V.19. N9. P.6671-6676. DOI: 10.1039/c6cp07721h WOS Scopus РИНЦ CAPlusCA OpenAlex

Полный текст от издателя

Поступила в редакцию:	11 нояб. 2016 г.
Принята к публикации:	2 февр. 2017 г.
Опубликована online:	2 февр. 2017 г.

Web of science:	WOS:000396031200036
Scopus:	2-s2.0-85018487116
РИНЦ:	31018606
Chemical Abstracts:	2017:199231
Chemical Abstracts (print):	166:294617
OpenAlex:	W2583914272

БД	Цитирований
Web of science	29
Scopus	30
OpenAlex	30