Photochemistry and Thermal Chemistry in Polymeric Ceramic Precursors
While pyrolysis of polymeric precursors has gained attention for the additive manufacturing of ceramics, the high-temperature process is energy-inefficient and time-consuming. Recently, photochemistry has been suggested to reduce energy consumption and reaction time, but the microscopic mechanisms o...
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2025
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| _version_ | 1852016695138320384 |
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| author | Nabankur Dasgupta (6416735) |
| author2 | Kai Ito (10347974) Thomas M. Linker (16807124) Wataru Sugimoto (1826413) Seyedmahmoud Mortazavi (22232929) Rajiv K. Kalia (1781878) Aiichiro Nakano (1403197) Alexander T. Radosevich (1555162) Kohei Shimamura (1656787) Fuyuki Shimojo (1448527) Adri van Duin (7125542) Priya Vashishta (1781872) |
| author2_role | author author author author author author author author author author author |
| author_facet | Nabankur Dasgupta (6416735) Kai Ito (10347974) Thomas M. Linker (16807124) Wataru Sugimoto (1826413) Seyedmahmoud Mortazavi (22232929) Rajiv K. Kalia (1781878) Aiichiro Nakano (1403197) Alexander T. Radosevich (1555162) Kohei Shimamura (1656787) Fuyuki Shimojo (1448527) Adri van Duin (7125542) Priya Vashishta (1781872) |
| author_role | author |
| dc.creator.none.fl_str_mv | Nabankur Dasgupta (6416735) Kai Ito (10347974) Thomas M. Linker (16807124) Wataru Sugimoto (1826413) Seyedmahmoud Mortazavi (22232929) Rajiv K. Kalia (1781878) Aiichiro Nakano (1403197) Alexander T. Radosevich (1555162) Kohei Shimamura (1656787) Fuyuki Shimojo (1448527) Adri van Duin (7125542) Priya Vashishta (1781872) |
| dc.date.none.fl_str_mv | 2025-09-11T18:56:19Z |
| dc.identifier.none.fl_str_mv | 10.1021/acs.jpclett.5c02429.s002 |
| dc.relation.none.fl_str_mv | https://figshare.com/articles/media/Photochemistry_and_Thermal_Chemistry_in_Polymeric_Ceramic_Precursors/30108514 |
| dc.rights.none.fl_str_mv | CC BY-NC 4.0 info:eu-repo/semantics/openAccess |
| dc.subject.none.fl_str_mv | Biophysics Biochemistry Medicine Genetics Molecular Biology Evolutionary Biology Inorganic Chemistry Computational Biology Biological Sciences not elsewhere classified Chemical Sciences not elsewhere classified photoexcitation causes scission multiscale simulation approach carbonyl carbon shifting precursor remains stable reveal distinct photochemical reduce energy consumption polymeric ceramic precursors longer time scales facile additive manufacturing ceramics toward achieving thermal reaction pathways polymeric precursors additive manufacturing thermal pathways reaction time acylsilane precursor thermal chemistry temperature process sustainable society sico clusters principles nonadiabatic photoexcited hole microscopic mechanisms many atoms mainly resulting initial stage gained attention design ultralow combines first |
| dc.title.none.fl_str_mv | Photochemistry and Thermal Chemistry in Polymeric Ceramic Precursors |
| dc.type.none.fl_str_mv | Dataset Media info:eu-repo/semantics/publishedVersion dataset |
| description | While pyrolysis of polymeric precursors has gained attention for the additive manufacturing of ceramics, the high-temperature process is energy-inefficient and time-consuming. Recently, photochemistry has been suggested to reduce energy consumption and reaction time, but the microscopic mechanisms of such accelerated reactions remain elusive. Here, we reveal distinct photochemical and thermal reaction pathways at the initial stage of silicon–carbide ceramic formation from an acylsilane precursor, using a multiscale simulation approach that combines first-principles nonadiabatic and adiabatic quantum molecular dynamics simulations with semiempirical reactive molecular dynamics simulations. While photoexcitation causes scission of Si–C bonds within 100 fs driven by the localization of a photoexcited hole, the precursor remains stable at high temperatures up to 1800 K without photoexcitation. On longer time scales, we find thermal reaction pathways involving concerted motions of many atoms, including the formation of SiCO clusters, mainly resulting from oxygen of carbonyl carbon shifting and bonding with silicon. This microscopic understanding suggests synergistic use of photochemical and thermal pathways to design ultralow-energy and facile additive manufacturing of ceramics toward achieving a sustainable society. |
| eu_rights_str_mv | openAccess |
| id | Manara_99b65f4e146e5b09da0c42f29b81e2ab |
| identifier_str_mv | 10.1021/acs.jpclett.5c02429.s002 |
| network_acronym_str | Manara |
| network_name_str | ManaraRepo |
| oai_identifier_str | oai:figshare.com:article/30108514 |
| publishDate | 2025 |
| repository.mail.fl_str_mv | |
| repository.name.fl_str_mv | |
| repository_id_str | |
| rights_invalid_str_mv | CC BY-NC 4.0 |
| spelling | Photochemistry and Thermal Chemistry in Polymeric Ceramic PrecursorsNabankur Dasgupta (6416735)Kai Ito (10347974)Thomas M. Linker (16807124)Wataru Sugimoto (1826413)Seyedmahmoud Mortazavi (22232929)Rajiv K. Kalia (1781878)Aiichiro Nakano (1403197)Alexander T. Radosevich (1555162)Kohei Shimamura (1656787)Fuyuki Shimojo (1448527)Adri van Duin (7125542)Priya Vashishta (1781872)BiophysicsBiochemistryMedicineGeneticsMolecular BiologyEvolutionary BiologyInorganic ChemistryComputational BiologyBiological Sciences not elsewhere classifiedChemical Sciences not elsewhere classifiedphotoexcitation causes scissionmultiscale simulation approachcarbonyl carbon shiftingprecursor remains stablereveal distinct photochemicalreduce energy consumptionpolymeric ceramic precursorslonger time scalesfacile additive manufacturingceramics toward achievingthermal reaction pathwayspolymeric precursorsadditive manufacturingthermal pathwaysreaction timeacylsilane precursorthermal chemistrytemperature processsustainable societysico clustersprinciples nonadiabaticphotoexcited holemicroscopic mechanismsmany atomsmainly resultinginitial stagegained attentiondesign ultralowcombines firstWhile pyrolysis of polymeric precursors has gained attention for the additive manufacturing of ceramics, the high-temperature process is energy-inefficient and time-consuming. Recently, photochemistry has been suggested to reduce energy consumption and reaction time, but the microscopic mechanisms of such accelerated reactions remain elusive. Here, we reveal distinct photochemical and thermal reaction pathways at the initial stage of silicon–carbide ceramic formation from an acylsilane precursor, using a multiscale simulation approach that combines first-principles nonadiabatic and adiabatic quantum molecular dynamics simulations with semiempirical reactive molecular dynamics simulations. While photoexcitation causes scission of Si–C bonds within 100 fs driven by the localization of a photoexcited hole, the precursor remains stable at high temperatures up to 1800 K without photoexcitation. On longer time scales, we find thermal reaction pathways involving concerted motions of many atoms, including the formation of SiCO clusters, mainly resulting from oxygen of carbonyl carbon shifting and bonding with silicon. This microscopic understanding suggests synergistic use of photochemical and thermal pathways to design ultralow-energy and facile additive manufacturing of ceramics toward achieving a sustainable society.2025-09-11T18:56:19ZDatasetMediainfo:eu-repo/semantics/publishedVersiondataset10.1021/acs.jpclett.5c02429.s002https://figshare.com/articles/media/Photochemistry_and_Thermal_Chemistry_in_Polymeric_Ceramic_Precursors/30108514CC BY-NC 4.0info:eu-repo/semantics/openAccessoai:figshare.com:article/301085142025-09-11T18:56:19Z |
| spellingShingle | Photochemistry and Thermal Chemistry in Polymeric Ceramic Precursors Nabankur Dasgupta (6416735) Biophysics Biochemistry Medicine Genetics Molecular Biology Evolutionary Biology Inorganic Chemistry Computational Biology Biological Sciences not elsewhere classified Chemical Sciences not elsewhere classified photoexcitation causes scission multiscale simulation approach carbonyl carbon shifting precursor remains stable reveal distinct photochemical reduce energy consumption polymeric ceramic precursors longer time scales facile additive manufacturing ceramics toward achieving thermal reaction pathways polymeric precursors additive manufacturing thermal pathways reaction time acylsilane precursor thermal chemistry temperature process sustainable society sico clusters principles nonadiabatic photoexcited hole microscopic mechanisms many atoms mainly resulting initial stage gained attention design ultralow combines first |
| status_str | publishedVersion |
| title | Photochemistry and Thermal Chemistry in Polymeric Ceramic Precursors |
| title_full | Photochemistry and Thermal Chemistry in Polymeric Ceramic Precursors |
| title_fullStr | Photochemistry and Thermal Chemistry in Polymeric Ceramic Precursors |
| title_full_unstemmed | Photochemistry and Thermal Chemistry in Polymeric Ceramic Precursors |
| title_short | Photochemistry and Thermal Chemistry in Polymeric Ceramic Precursors |
| title_sort | Photochemistry and Thermal Chemistry in Polymeric Ceramic Precursors |
| topic | Biophysics Biochemistry Medicine Genetics Molecular Biology Evolutionary Biology Inorganic Chemistry Computational Biology Biological Sciences not elsewhere classified Chemical Sciences not elsewhere classified photoexcitation causes scission multiscale simulation approach carbonyl carbon shifting precursor remains stable reveal distinct photochemical reduce energy consumption polymeric ceramic precursors longer time scales facile additive manufacturing ceramics toward achieving thermal reaction pathways polymeric precursors additive manufacturing thermal pathways reaction time acylsilane precursor thermal chemistry temperature process sustainable society sico clusters principles nonadiabatic photoexcited hole microscopic mechanisms many atoms mainly resulting initial stage gained attention design ultralow combines first |