Quantum-chemical investigation on the pre-nucleation cluster formation between oxalic acid conformers and atmospheric nucleation precursors
Aerosol particles formed in the Earth’s troposphere through the nucleation process have large impact on the planet’s radiative balance, cloud formation and precipitation patterns. The growing concerns about the climate change occurring in different parts of the world serve as a motivation for the sc...
| Autor principal: | Carvalho, Eduardo da Silva |
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| Outros Autores: | https://lattes.cnpq.br/6994516424394370 |
| Grau: | Dissertação |
| Idioma: | eng |
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Universidade Federal do Amazonas
2025
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https://tede.ufam.edu.br/handle/tede/10668 |
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oai:https:--tede.ufam.edu.br-handle-:tede-106682025-02-13T05:08:04Z Quantum-chemical investigation on the pre-nucleation cluster formation between oxalic acid conformers and atmospheric nucleation precursors Carvalho, Eduardo da Silva Chaudhuri, Puspitapallab https://lattes.cnpq.br/6994516424394370 http://lattes.cnpq.br/7716968611856757 Trichês, Daniela Menegon Canuto, Sylvio Roberto Accioly Ácido oxálico Ligação de hidrogênio Ligações químicas CIENCIAS EXATAS E DA TERRA: FISICA Oxalic acid Hydrogen bond DFT Molecular cluster Ácido oxálico Ligação de hidrogênio Molecular cluster Aerosol particles formed in the Earth’s troposphere through the nucleation process have large impact on the planet’s radiative balance, cloud formation and precipitation patterns. The growing concerns about the climate change occurring in different parts of the world serve as a motivation for the scientific community to study the formation processes and physicochemical properties of atmospheric aerosols. Oxalic acid is one of the simplest naturally occurring dicarboxylic acid that is abundantly found in the atmosphere, and it has several stable structural conformers. Hydrogen-bonded interactions of oxalic acid with other atmospheric molecules are important as they might influence the chemical composition of the atmosphere, thereby impacting atmospheric chemistry and environmental processes. In this work, we used Density Functional calculations with the M06-2X/6-311++G(3df,3pd) model to examine the interaction of different oxalic acid conformers with sulfuric acid and ammonia — two widely recognized atmospheric nucleation precursor molecules — with the aim of observing the hydrogen bonding characteristics of the conformers individually. An extensive and systematic quantum-chemical calculation has been conducted to analyze the structural, thermodynamical, electrical, and spectroscopic characteristics of several binary and ternary clusters mediated by five oxalic acid conformers. Our analysis of the electronic binding energies and free energy changes associated with the formation of clusters and its population distribution at ambient temperature reveals that multiple conformations of oxalic acid have the potential to engage in stable cluster formation in the atmosphere. In fact, the highest energy oxalic acid conformer contributes most significantly to the population distribution of the clusters. According to the present calculations, clusters of oxalic acid with sulfuric acid demonstrate greater thermodynamic stability, a higher probability of formation, and more intense light scattering compared to clusters with ammonia. Furthermore, the analysis of successive cluster formation reveals that clusters formed between sulfuric acid and oxalic acid are more likely to grow spontaneously than those formed between ammonia and oxalic acid. Partículas de aerossol formadas na troposfera terrestre através do processo de nucleação têm um grande impacto no balanço radiativo do planeta, na formação de nuvens e nos padrões de precipitação. As crescentes preocupações com as mudanças climáticas em diferentes partes do mundo servem como motivação para a comunidade científica estudar os processos de formação e as propriedades físico-químicas dos aerossóis atmosféricos. O ácido oxálico é um dos ácidos dicarboxílicos mais simples e naturalmente presentes na atmosfera, sendo encontrado em abundância e apresentando vários conformações estruturais estáveis. As interações do ácido oxálico, mediadas por ligações de hidrogênio, com outras moléculas atmosféricas são importantes, pois podem influenciar a composição química da atmosfera, impactando assim a físico-química atmosférica e os processos ambientais. Neste trabalho, realizamos cálculos de Teoria do Funcional da Densidade com o modelo M06-2X/6-311++G(3df,3pd) para examinar a interação de diferentes conformações do ácido oxálico com ácido sulfúrico e amônia — duas moléculas amplamente reconhecidas como precursoras da nucleação atmosférica — com o objetivo de observar as características das ligação de hidrogênio das conformações individuais. Uma extensa e sistemática análise químico-quântica foi conduzida para analisar as características estruturais, termodinâmicas, elétricas e espectroscópicas de vários aglomerados binários e ternários mediados por cinco conformações do ácido oxálico. Nossa análise das energias de ligação eletrônica e das variações na energia livre associadas à formação de aglomerados e sua distribuição populacional em temperatura ambiente revela que múltiplas conformações do ácido oxálico têm potencial para formar aglomerados estáveis na atmosfera. De fato, a conformação de ácido oxálico de maior energia contribui de forma mais significativa para a distribuição populacional dos aglomerados. De acordo com os cálculos realizados, os aglomerados de ácido oxálico com ácido sulfúrico apresentam maior estabilidade termodinâmica e maior intensidade de espalhamento de luz em comparação com aqueles formados com amônia. Além disso, a análise da formação sucessiva de aglomerados revela que os aglomerados formados entre o ácido sulfúrico e o ácido oxálico têm maior probabilidade de crescer espontaneamente do que aqueles formados entre a amônia e o ácido oxálico. CAPES - Coordenação de Aperfeiçoamento de Pessoal de Nível Superior 2025-02-12T19:30:43Z 2024-09-23 Dissertação CARVALHO, Eduardo da Silva. Quantum-chemical investigation on the pre-nucleation cluster formation between oxalic acid conformers and atmospheric nucleation precursors. 2024. 80 f. Dissertação (Mestrado em Física) - Universidade Federal do Amazonas, Manaus, 2024. https://tede.ufam.edu.br/handle/tede/10668 eng Acesso Aberto https://creativecommons.org/licenses/by-nc-nd/4.0/ application/pdf Universidade Federal do Amazonas Instituto de Ciências Exatas Brasil UFAM Programa de Pós-graduação em Física |
| institution |
TEDE - Universidade Federal do Amazonas |
| collection |
TEDE-UFAM |
| language |
eng |
| topic |
Ácido oxálico Ligação de hidrogênio Ligações químicas CIENCIAS EXATAS E DA TERRA: FISICA Oxalic acid Hydrogen bond DFT Molecular cluster Ácido oxálico Ligação de hidrogênio Molecular cluster |
| spellingShingle |
Ácido oxálico Ligação de hidrogênio Ligações químicas CIENCIAS EXATAS E DA TERRA: FISICA Oxalic acid Hydrogen bond DFT Molecular cluster Ácido oxálico Ligação de hidrogênio Molecular cluster Carvalho, Eduardo da Silva Quantum-chemical investigation on the pre-nucleation cluster formation between oxalic acid conformers and atmospheric nucleation precursors |
| topic_facet |
Ácido oxálico Ligação de hidrogênio Ligações químicas CIENCIAS EXATAS E DA TERRA: FISICA Oxalic acid Hydrogen bond DFT Molecular cluster Ácido oxálico Ligação de hidrogênio Molecular cluster |
| description |
Aerosol particles formed in the Earth’s troposphere through the nucleation process have large impact on the planet’s radiative balance, cloud formation and precipitation patterns. The growing concerns about the climate change occurring in different parts of the world serve as a motivation for the scientific community to study the formation processes and physicochemical properties of atmospheric aerosols. Oxalic acid is one of the simplest naturally occurring dicarboxylic acid that is abundantly found in the atmosphere, and it has several stable structural conformers. Hydrogen-bonded interactions of oxalic acid with other atmospheric molecules are important as they might influence the chemical composition of the atmosphere, thereby impacting atmospheric chemistry and environmental processes. In this work, we used Density Functional calculations with the M06-2X/6-311++G(3df,3pd) model to examine the interaction of different oxalic acid conformers with sulfuric acid and ammonia — two widely recognized atmospheric nucleation precursor molecules — with the aim of observing the hydrogen bonding characteristics of the conformers individually. An extensive and systematic quantum-chemical calculation has been conducted to analyze the structural, thermodynamical, electrical, and spectroscopic characteristics of several binary and ternary clusters mediated by five oxalic acid conformers. Our analysis of the electronic binding energies and free energy changes associated with the formation of clusters and its population distribution at ambient temperature reveals that multiple conformations of oxalic acid have the potential to engage in stable cluster formation in the atmosphere. In fact, the highest energy oxalic acid conformer contributes most significantly to the population distribution of the clusters. According to the present calculations, clusters of oxalic acid with sulfuric acid demonstrate greater thermodynamic stability, a higher probability of formation, and more intense light scattering compared to clusters with ammonia. Furthermore, the analysis of successive cluster formation reveals that clusters formed between sulfuric acid and oxalic acid are more likely to grow spontaneously than those formed between ammonia and oxalic acid. |
| author_additional |
Chaudhuri, Puspitapallab |
| author_additionalStr |
Chaudhuri, Puspitapallab |
| format |
Dissertação |
| author |
Carvalho, Eduardo da Silva |
| author2 |
https://lattes.cnpq.br/6994516424394370 |
| author2Str |
https://lattes.cnpq.br/6994516424394370 |
| title |
Quantum-chemical investigation on the pre-nucleation cluster formation between oxalic acid conformers and atmospheric nucleation precursors |
| title_short |
Quantum-chemical investigation on the pre-nucleation cluster formation between oxalic acid conformers and atmospheric nucleation precursors |
| title_full |
Quantum-chemical investigation on the pre-nucleation cluster formation between oxalic acid conformers and atmospheric nucleation precursors |
| title_fullStr |
Quantum-chemical investigation on the pre-nucleation cluster formation between oxalic acid conformers and atmospheric nucleation precursors |
| title_full_unstemmed |
Quantum-chemical investigation on the pre-nucleation cluster formation between oxalic acid conformers and atmospheric nucleation precursors |
| title_sort |
quantum-chemical investigation on the pre-nucleation cluster formation between oxalic acid conformers and atmospheric nucleation precursors |
| publisher |
Universidade Federal do Amazonas |
| publishDate |
2025 |
| url |
https://tede.ufam.edu.br/handle/tede/10668 |
| _version_ |
1831970403728228352 |
| score |
11.753896 |