Role of Optical Phonons and Anharmonicity in the Appearance of the Heat Capacity Boson Peak-like Anomaly in Fully Ordered Molecular Crystals

We demonstrate that the heat capacity Boson peak (BP)-like anomaly appearing in fully ordered anharmonic molecular crystals emerges as a result of the strong interactions between propagating (acoustic) and low-energy quasi-localized (optical) phonons. In particular, we experimentally determine the l...

Full description

Saved in:
Bibliographic Details
Published in:The journal of physical chemistry letters 2022-06, Vol.13 (22), p.5061-5067
Main Authors: Krivchikov, Alexander I., Jeżowski, Andrezj, Szewczyk, Daria, Korolyuk, Oxsana A., Romantsova, Olesya O., Buravtseva, Lubov M., Cazorla, Claudio, Tamarit, Josep Ll
Format: Article
Language:English
Subjects:
Letter
Physical Insights into Materials and Molecular Properties
Citations: Items that this one cites
Items that cite this one
Online Access:Get full text
Tags: Add Tag
No Tags, Be the first to tag this record!
cited_by cdi_FETCH-LOGICAL-a445t-8b210a30b02dd994480c36e647b2c2b57332df51bd1372e8f794b573bc940a3e3
cites cdi_FETCH-LOGICAL-a445t-8b210a30b02dd994480c36e647b2c2b57332df51bd1372e8f794b573bc940a3e3
container_end_page 5067
container_issue 22
container_start_page 5061
container_title The journal of physical chemistry letters
container_volume 13
creator Krivchikov, Alexander I.
Jeżowski, Andrezj
Szewczyk, Daria
Korolyuk, Oxsana A.
Romantsova, Olesya O.
Buravtseva, Lubov M.
Cazorla, Claudio
Tamarit, Josep Ll
description We demonstrate that the heat capacity Boson peak (BP)-like anomaly appearing in fully ordered anharmonic molecular crystals emerges as a result of the strong interactions between propagating (acoustic) and low-energy quasi-localized (optical) phonons. In particular, we experimentally determine the low-temperature (
doi_str_mv 10.1021/acs.jpclett.2c01224
format article
fullrecord <record><control><sourceid>proquest_pubme</sourceid><recordid>TN_cdi_pubmedcentral_primary_oai_pubmedcentral_nih_gov_9189925</recordid><sourceformat>XML</sourceformat><sourcesystem>PC</sourcesystem><sourcerecordid>2672704942</sourcerecordid><originalsourceid>FETCH-LOGICAL-a445t-8b210a30b02dd994480c36e647b2c2b57332df51bd1372e8f794b573bc940a3e3</originalsourceid><addsrcrecordid>eNp9kctuFDEQRS1ERELIFyAhL9n0xHa7H94gDSNCkBJNhMjaqna7GSduu7HdkeYf-Gg8D6KwYVWl8j23Sr4IvadkQQmjl6Di4mFSVqe0YIpQxvgrdEYFb4uGttXrF_0pehvjAyG1IG3zBp2WVV0xQegZ-v3dW439gNdTMgosvtt4513E4Hq8dBsIo3dGmbTFxuG00Xg5TRoCOLXHdpNrDQmvYIK97LOP3uE7DY-FNY9Z7_wIdo9fzTY369DroHt8mzer2ULAq7CNCWx8h06GXPTFsZ6j-6svP1bXxc3667fV8qYAzqtUtB2jBErSEdb3QnDeElXWuuZNxxTrqqYsWT9UtOtp2TDdDo3gu2mnBM-cLs_Rp4PvNHej7pV2KYCVUzAjhK30YOS_L85s5E__JAVthWBVNvh4NAj-16xjkqOJSlsLTvs5SlY3rCFccJal5UGqgo8x6OF5DSVyl6PMOcpjjvKYY6Y-vLzwmfkbXBZcHgR72s_B5Q_7r-UfdQmujw</addsrcrecordid><sourcetype>Open Access Repository</sourcetype><iscdi>true</iscdi><recordtype>article</recordtype><pqid>2672704942</pqid></control><display><type>article</type><title>Role of Optical Phonons and Anharmonicity in the Appearance of the Heat Capacity Boson Peak-like Anomaly in Fully Ordered Molecular Crystals</title><source>American Chemical Society:Jisc Collections:American Chemical Society Read &amp; Publish Agreement 2022-2024 (Reading list)</source><creator>Krivchikov, Alexander I. ; Jeżowski, Andrezj ; Szewczyk, Daria ; Korolyuk, Oxsana A. ; Romantsova, Olesya O. ; Buravtseva, Lubov M. ; Cazorla, Claudio ; Tamarit, Josep Ll</creator><creatorcontrib>Krivchikov, Alexander I. ; Jeżowski, Andrezj ; Szewczyk, Daria ; Korolyuk, Oxsana A. ; Romantsova, Olesya O. ; Buravtseva, Lubov M. ; Cazorla, Claudio ; Tamarit, Josep Ll</creatorcontrib><description>We demonstrate that the heat capacity Boson peak (BP)-like anomaly appearing in fully ordered anharmonic molecular crystals emerges as a result of the strong interactions between propagating (acoustic) and low-energy quasi-localized (optical) phonons. In particular, we experimentally determine the low-temperature (&lt;30 K) specific heat of the molecular crystal benzophenone and those of several of its fully ordered bromine derivatives. Subsequently, by means of theoretical first-principles methods based on density functional theory, we estimate the corresponding phonon dispersions and vibrational density of states. Our results reveal two possible mechanisms for the emergence of the BP-like anomaly: (i) acoustic–optic phonon avoided crossing, which gives rise to a pseudo-van Hove singularity in the acoustic phonon branches, and (ii) piling up of low-frequency optical phonons, which are quasi degenerate with longitudinal acoustic modes and lead to a surge in the vibrational density of states at low energies.</description><identifier>ISSN: 1948-7185</identifier><identifier>EISSN: 1948-7185</identifier><identifier>DOI: 10.1021/acs.jpclett.2c01224</identifier><identifier>PMID: 35652901</identifier><language>eng</language><publisher>United States: American Chemical Society</publisher><subject>Letter ; Physical Insights into Materials and Molecular Properties</subject><ispartof>The journal of physical chemistry letters, 2022-06, Vol.13 (22), p.5061-5067</ispartof><rights>2022 The Authors. Published by American Chemical Society</rights><rights>2022 The Authors. Published by American Chemical Society 2022 The Authors</rights><lds50>peer_reviewed</lds50><oa>free_for_read</oa><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-a445t-8b210a30b02dd994480c36e647b2c2b57332df51bd1372e8f794b573bc940a3e3</citedby><cites>FETCH-LOGICAL-a445t-8b210a30b02dd994480c36e647b2c2b57332df51bd1372e8f794b573bc940a3e3</cites><orcidid>0000-0001-7923-1239 ; 0000-0002-6501-4513 ; 0000-0002-7965-0000</orcidid></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>230,314,780,784,885,27924,27925</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/35652901$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Krivchikov, Alexander I.</creatorcontrib><creatorcontrib>Jeżowski, Andrezj</creatorcontrib><creatorcontrib>Szewczyk, Daria</creatorcontrib><creatorcontrib>Korolyuk, Oxsana A.</creatorcontrib><creatorcontrib>Romantsova, Olesya O.</creatorcontrib><creatorcontrib>Buravtseva, Lubov M.</creatorcontrib><creatorcontrib>Cazorla, Claudio</creatorcontrib><creatorcontrib>Tamarit, Josep Ll</creatorcontrib><title>Role of Optical Phonons and Anharmonicity in the Appearance of the Heat Capacity Boson Peak-like Anomaly in Fully Ordered Molecular Crystals</title><title>The journal of physical chemistry letters</title><addtitle>J. Phys. Chem. Lett</addtitle><description>We demonstrate that the heat capacity Boson peak (BP)-like anomaly appearing in fully ordered anharmonic molecular crystals emerges as a result of the strong interactions between propagating (acoustic) and low-energy quasi-localized (optical) phonons. In particular, we experimentally determine the low-temperature (&lt;30 K) specific heat of the molecular crystal benzophenone and those of several of its fully ordered bromine derivatives. Subsequently, by means of theoretical first-principles methods based on density functional theory, we estimate the corresponding phonon dispersions and vibrational density of states. Our results reveal two possible mechanisms for the emergence of the BP-like anomaly: (i) acoustic–optic phonon avoided crossing, which gives rise to a pseudo-van Hove singularity in the acoustic phonon branches, and (ii) piling up of low-frequency optical phonons, which are quasi degenerate with longitudinal acoustic modes and lead to a surge in the vibrational density of states at low energies.</description><subject>Letter</subject><subject>Physical Insights into Materials and Molecular Properties</subject><issn>1948-7185</issn><issn>1948-7185</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2022</creationdate><recordtype>article</recordtype><recordid>eNp9kctuFDEQRS1ERELIFyAhL9n0xHa7H94gDSNCkBJNhMjaqna7GSduu7HdkeYf-Gg8D6KwYVWl8j23Sr4IvadkQQmjl6Di4mFSVqe0YIpQxvgrdEYFb4uGttXrF_0pehvjAyG1IG3zBp2WVV0xQegZ-v3dW439gNdTMgosvtt4513E4Hq8dBsIo3dGmbTFxuG00Xg5TRoCOLXHdpNrDQmvYIK97LOP3uE7DY-FNY9Z7_wIdo9fzTY369DroHt8mzer2ULAq7CNCWx8h06GXPTFsZ6j-6svP1bXxc3667fV8qYAzqtUtB2jBErSEdb3QnDeElXWuuZNxxTrqqYsWT9UtOtp2TDdDo3gu2mnBM-cLs_Rp4PvNHej7pV2KYCVUzAjhK30YOS_L85s5E__JAVthWBVNvh4NAj-16xjkqOJSlsLTvs5SlY3rCFccJal5UGqgo8x6OF5DSVyl6PMOcpjjvKYY6Y-vLzwmfkbXBZcHgR72s_B5Q_7r-UfdQmujw</recordid><startdate>20220609</startdate><enddate>20220609</enddate><creator>Krivchikov, Alexander I.</creator><creator>Jeżowski, Andrezj</creator><creator>Szewczyk, Daria</creator><creator>Korolyuk, Oxsana A.</creator><creator>Romantsova, Olesya O.</creator><creator>Buravtseva, Lubov M.</creator><creator>Cazorla, Claudio</creator><creator>Tamarit, Josep Ll</creator><general>American Chemical Society</general><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7X8</scope><scope>5PM</scope><orcidid>https://orcid.org/0000-0001-7923-1239</orcidid><orcidid>https://orcid.org/0000-0002-6501-4513</orcidid><orcidid>https://orcid.org/0000-0002-7965-0000</orcidid></search><sort><creationdate>20220609</creationdate><title>Role of Optical Phonons and Anharmonicity in the Appearance of the Heat Capacity Boson Peak-like Anomaly in Fully Ordered Molecular Crystals</title><author>Krivchikov, Alexander I. ; Jeżowski, Andrezj ; Szewczyk, Daria ; Korolyuk, Oxsana A. ; Romantsova, Olesya O. ; Buravtseva, Lubov M. ; Cazorla, Claudio ; Tamarit, Josep Ll</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-a445t-8b210a30b02dd994480c36e647b2c2b57332df51bd1372e8f794b573bc940a3e3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2022</creationdate><topic>Letter</topic><topic>Physical Insights into Materials and Molecular Properties</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Krivchikov, Alexander I.</creatorcontrib><creatorcontrib>Jeżowski, Andrezj</creatorcontrib><creatorcontrib>Szewczyk, Daria</creatorcontrib><creatorcontrib>Korolyuk, Oxsana A.</creatorcontrib><creatorcontrib>Romantsova, Olesya O.</creatorcontrib><creatorcontrib>Buravtseva, Lubov M.</creatorcontrib><creatorcontrib>Cazorla, Claudio</creatorcontrib><creatorcontrib>Tamarit, Josep Ll</creatorcontrib><collection>PubMed</collection><collection>CrossRef</collection><collection>MEDLINE - Academic</collection><collection>PubMed Central (Full Participant titles)</collection><jtitle>The journal of physical chemistry letters</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Krivchikov, Alexander I.</au><au>Jeżowski, Andrezj</au><au>Szewczyk, Daria</au><au>Korolyuk, Oxsana A.</au><au>Romantsova, Olesya O.</au><au>Buravtseva, Lubov M.</au><au>Cazorla, Claudio</au><au>Tamarit, Josep Ll</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Role of Optical Phonons and Anharmonicity in the Appearance of the Heat Capacity Boson Peak-like Anomaly in Fully Ordered Molecular Crystals</atitle><jtitle>The journal of physical chemistry letters</jtitle><addtitle>J. Phys. Chem. Lett</addtitle><date>2022-06-09</date><risdate>2022</risdate><volume>13</volume><issue>22</issue><spage>5061</spage><epage>5067</epage><pages>5061-5067</pages><issn>1948-7185</issn><eissn>1948-7185</eissn><abstract>We demonstrate that the heat capacity Boson peak (BP)-like anomaly appearing in fully ordered anharmonic molecular crystals emerges as a result of the strong interactions between propagating (acoustic) and low-energy quasi-localized (optical) phonons. In particular, we experimentally determine the low-temperature (&lt;30 K) specific heat of the molecular crystal benzophenone and those of several of its fully ordered bromine derivatives. Subsequently, by means of theoretical first-principles methods based on density functional theory, we estimate the corresponding phonon dispersions and vibrational density of states. Our results reveal two possible mechanisms for the emergence of the BP-like anomaly: (i) acoustic–optic phonon avoided crossing, which gives rise to a pseudo-van Hove singularity in the acoustic phonon branches, and (ii) piling up of low-frequency optical phonons, which are quasi degenerate with longitudinal acoustic modes and lead to a surge in the vibrational density of states at low energies.</abstract><cop>United States</cop><pub>American Chemical Society</pub><pmid>35652901</pmid><doi>10.1021/acs.jpclett.2c01224</doi><tpages>7</tpages><orcidid>https://orcid.org/0000-0001-7923-1239</orcidid><orcidid>https://orcid.org/0000-0002-6501-4513</orcidid><orcidid>https://orcid.org/0000-0002-7965-0000</orcidid><oa>free_for_read</oa></addata></record>
fulltext fulltext
identifier ISSN: 1948-7185
ispartof The journal of physical chemistry letters, 2022-06, Vol.13 (22), p.5061-5067
issn 1948-7185
1948-7185
language eng
recordid cdi_pubmedcentral_primary_oai_pubmedcentral_nih_gov_9189925
source American Chemical Society:Jisc Collections:American Chemical Society Read & Publish Agreement 2022-2024 (Reading list)
subjects Letter
Physical Insights into Materials and Molecular Properties
title Role of Optical Phonons and Anharmonicity in the Appearance of the Heat Capacity Boson Peak-like Anomaly in Fully Ordered Molecular Crystals
url http://sfxeu10.hosted.exlibrisgroup.com/loughborough?ctx_ver=Z39.88-2004&ctx_enc=info:ofi/enc:UTF-8&ctx_tim=2025-01-01T09%3A42%3A49IST&url_ver=Z39.88-2004&url_ctx_fmt=infofi/fmt:kev:mtx:ctx&rfr_id=info:sid/primo.exlibrisgroup.com:primo3-Article-proquest_pubme&rft_val_fmt=info:ofi/fmt:kev:mtx:journal&rft.genre=article&rft.atitle=Role%20of%20Optical%20Phonons%20and%20Anharmonicity%20in%20the%20Appearance%20of%20the%20Heat%20Capacity%20Boson%20Peak-like%20Anomaly%20in%20Fully%20Ordered%20Molecular%20Crystals&rft.jtitle=The%20journal%20of%20physical%20chemistry%20letters&rft.au=Krivchikov,%20Alexander%20I.&rft.date=2022-06-09&rft.volume=13&rft.issue=22&rft.spage=5061&rft.epage=5067&rft.pages=5061-5067&rft.issn=1948-7185&rft.eissn=1948-7185&rft_id=info:doi/10.1021/acs.jpclett.2c01224&rft_dat=%3Cproquest_pubme%3E2672704942%3C/proquest_pubme%3E%3Cgrp_id%3Ecdi_FETCH-LOGICAL-a445t-8b210a30b02dd994480c36e647b2c2b57332df51bd1372e8f794b573bc940a3e3%3C/grp_id%3E%3Coa%3E%3C/oa%3E%3Curl%3E%3C/url%3E&rft_id=info:oai/&rft_pqid=2672704942&rft_id=info:pmid/35652901&rfr_iscdi=true