On the Predictive Power of Chemical Concepts

AbstractLithium-ion batteries (LIBs) represent the state of the art in high-density energy storage. To further advance LIB technology, a fundamental understanding of the underlying chemical processes is required. In particular, the decomposition of electrolyte species and associated formation of the solid electrolyte interphase (SEI) is critical for LIB performance. However, SEI formation is poorly understood, in part due to insufficient exploration of the vast reactive space. The Lithium-Ion Battery Electrolyte (LIBE) dataset reported here aims to provide accurate first-principles data to improve the understanding of SEI species and associated reactions. The dataset was generated by fragmenting a set of principal molecules, including solvents, salts, and SEI products, and then selectively recombining a subset of the fragments. All candidate molecules were analyzed at the ωB97X-V/def2-TZVPPD/SMD level of theory at various charges and spin multiplicities. In total, LIBE contains structural, thermodynamic, and vibrational information on over 17,000 unique species. In addition to studies of reactivity in LIBs, this dataset may prove useful for machine learning of molecular and reaction properties.

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Quantum Chemical Calculations of Lithium-Ion Battery Electrolyte and Interphase Species

10.26434/chemrxiv.14226542.v2 ◽

2021 ◽

Author(s):

Evan Walter Clark Spotte-Smith ◽

Samuel Blau ◽

Xiaowei Xie ◽

Hetal Patel ◽

Mingjian Wen ◽

...

Keyword(s):

Lithium Ion Battery ◽

First Principles ◽

Quantum Chemical ◽

State Of The Art ◽

Solid Electrolyte Interphase ◽

Lithium Ion ◽

Chemical Processes ◽

Fundamental Understanding ◽

Battery Electrolyte ◽

Unique Species

Lithium-ion batteries (LIBs) represent the state of the art in high-density energy storage. To further advance LIB technology, a fundamental understanding of the underlying chemical processes is required. In particular, the decomposition of electrolyte species and associated formation of the solid electrolyte interphase (SEI) is critical for LIB performance. However, SEI formation is poorly understood, in part due to insufficient exploration of the vast reactive space. The Lithium-Ion Battery Electrolyte(LIBE) dataset reported here aims to provide accurate first-principles data to improve the understanding of SEI species and associated reactions. The dataset was generated by fragmenting a set of principal molecules, including solvents, salts, and SEI products, and then selectively recombining a subset of the fragments. All candidate molecules were analyzed at the ωB97X-V/def2-TZVPPD/SMD level of theory at various charges and spin multiplicities. In total, LIBE contains structural,thermodynamic, and vibrational information on over 17,000 unique species. In addition to studies of reactivity in LIBs, this dataset may prove useful for machine learning of molecular and reaction properties.

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Quantum Chemical Calculations of Lithium-Ion Battery Electrolyte and Interphase Species

10.26434/chemrxiv.14226542.v3 ◽

2021 ◽

Author(s):

Evan Walter Clark Spotte-Smith ◽

Samuel Blau ◽

Xiaowei Xie ◽

Hetal Patel ◽

Mingjian Wen ◽

...

Keyword(s):

Lithium Ion Battery ◽

First Principles ◽

Quantum Chemical ◽

State Of The Art ◽

Solid Electrolyte Interphase ◽

Lithium Ion ◽

Chemical Processes ◽

Fundamental Understanding ◽

Battery Electrolyte ◽

Unique Species

Lithium-ion batteries (LIBs) represent the state of the art in high-density energy storage. To further advance LIB technology, a fundamental understanding of the underlying chemical processes is required. In particular, the decomposition of electrolyte species and associated formation of the solid electrolyte interphase (SEI) is critical for LIB performance. However, SEI formation is poorly understood, in part due to insufficient exploration of the vast reactive space. The Lithium-Ion Battery Electrolyte(LIBE) dataset reported here aims to provide accurate first-principles data to improve the understanding of SEI species and associated reactions. The dataset was generated by fragmenting a set of principal molecules, including solvents, salts, and SEI products, and then selectively recombining a subset of the fragments. All candidate molecules were analyzed at the ωB97X-V/def2-TZVPPD/SMD level of theory at various charges and spin multiplicities. In total, LIBE contains structural,thermodynamic, and vibrational information on over 17,000 unique species. In addition to studies of reactivity in LIBs, this dataset may prove useful for machine learning of molecular and reaction properties.

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On Semi-Classical Approach to Materials Electronic Structure

Journal of Material Science and Technology Research ◽

10.31875/2410-4701.2021.08.6 ◽

2021 ◽

Vol 8 ◽

pp. 41-49

Author(s):

Levan Chkhartishvili

Keyword(s):

Electronic Structure ◽

Ground State ◽

First Principles ◽

Predictive Power ◽

Materials Science ◽

Special Functions ◽

Chemical Reactivity ◽

Classical Model ◽

Functional Materials ◽

Classical Approach

Materials atomic structure, ground-state and physical properties as well as their chemical reactivity mainly are determined by electronic structure. When first-principles methods of studying the electronic structure acquire good predictive power, the best approach would be to design new functional materials theoretically and then check experimentally only most perspective ones. In the paper, the semi-classical model of multi-electron atom is constructed, which makes it possible to calculate analytically (in special functions) the electronic structure of atomic particles themselves and materials as their associated systems. Expected relative accuracy makes a few percent, what is quite acceptable for materials science purposes.

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Quantum Chemical Calculations of Lithium-Ion Battery Electrolyte and Interphase Species

10.26434/chemrxiv.14226542.v1 ◽

2021 ◽

Author(s):

Evan Walter Clark Spotte-Smith ◽

Samuel Blau ◽

Xiaowei Xie ◽

Hetal Patel ◽

Mingjian Wen ◽

...

Keyword(s):

Lithium Ion Battery ◽

First Principles ◽

Quantum Chemical ◽

State Of The Art ◽

Solid Electrolyte Interphase ◽

Lithium Ion ◽

Chemical Processes ◽

Fundamental Understanding ◽

Battery Electrolyte ◽

Unique Species

Lithium-ion batteries (LIBs) represent the state of the art in high-density energy storage. To further advance LIB technology, a fundamental understanding of the underlying chemical processes is required. In particular, the decomposition of electrolyte species and associated formation of the solid electrolyte interphase (SEI) is critical for LIB performance. However, SEI formation is poorly understood, in part due to insufficient exploration of the vast reactive space. The Lithium-Ion Battery Electrolyte(LIBE) dataset reported here aims to provide accurate first-principles data to improve the understanding of SEI species and associated reactions. The dataset was generated by fragmenting a set of principal molecules, including solvents, salts, and SEI products, and then selectively recombining a subset of the fragments. All candidate molecules were analyzed at theωB97X-V/def2-TZVPPD/SMD level of theory at various charges and spin multiplicities. In total, LIBE contains structural,thermodynamic, and vibrational information on over 17,000 unique species. In addition to studies of reactivity in LIBs, this dataset may prove useful for machine learning of molecular and reaction properties.

Download Full-text

Quantum Chemical Calculations of Lithium-Ion Battery Electrolyte and Interphase Species

10.26434/chemrxiv.14226542 ◽

2021 ◽

Author(s):

Evan Walter Clark Spotte-Smith ◽

Samuel Blau ◽

Xiaowei Xie ◽

Hetal Patel ◽

Mingjian Wen ◽

...

Keyword(s):

Lithium Ion Battery ◽

First Principles ◽

Quantum Chemical ◽

State Of The Art ◽

Solid Electrolyte Interphase ◽

Lithium Ion ◽

Chemical Processes ◽

Fundamental Understanding ◽

Battery Electrolyte ◽

Unique Species

Lithium-ion batteries (LIBs) represent the state of the art in high-density energy storage. To further advance LIB technology, a fundamental understanding of the underlying chemical processes is required. In particular, the decomposition of electrolyte species and associated formation of the solid electrolyte interphase (SEI) is critical for LIB performance. However, SEI formation is poorly understood, in part due to insufficient exploration of the vast reactive space. The Lithium-Ion Battery Electrolyte(LIBE) dataset reported here aims to provide accurate first-principles data to improve the understanding of SEI species and associated reactions. The dataset was generated by fragmenting a set of principal molecules, including solvents, salts, and SEI products, and then selectively recombining a subset of the fragments. All candidate molecules were analyzed at theωB97X-V/def2-TZVPPD/SMD level of theory at various charges and spin multiplicities. In total, LIBE contains structural,thermodynamic, and vibrational information on over 17,000 unique species. In addition to studies of reactivity in LIBs, this dataset may prove useful for machine learning of molecular and reaction properties.

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Translation Research for the Rehabilitation of Left Spatial Neglect and Associated Disorders of Attention in Stroke Patients

Perspectives on Neurophysiology and Neurogenic Speech and Language Disorders ◽

10.1044/nnsld18.2.55 ◽

2008 ◽

Vol 18 (2) ◽

pp. 55-65 ◽

Cited By ~ 2

Author(s):

Nkiruka Arene ◽

Argye E. Hillis

Keyword(s):

Theoretical Basis ◽

Attention Bias ◽

Spatial Neglect ◽

Clinical Use ◽

Stroke Patients ◽

Translation Research ◽

Unilateral Neglect ◽

Assessment And Treatment ◽

Sound Theoretical Basis ◽

Review Current

Abstract The syndrome of unilateral neglect, typified by a lateralized attention bias and neglect of contralateral space, is an important cause of morbidity and disability after a stroke. In this review, we discuss the challenges that face researchers attempting to elucidate the mechanisms and effectiveness of rehabilitation treatments. The neglect syndrome is a heterogeneous disorder, and it is not clear which of its symptoms cause ongoing disability. We review current methods of neglect assessment and propose logical approaches to selecting treatments, while acknowledging that further study is still needed before some of these approaches can be translated into routine clinical use. We conclude with systems-level suggestions for hypothesis development that would hopefully form a sound theoretical basis for future approaches to the assessment and treatment of neglect.

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Computationally Augmented Retrosynthesis: Total Synthesis of Paspaline A and Emindole PB

10.26434/chemrxiv.7322330.v1 ◽

2018 ◽

Author(s):

Timothy Newhouse ◽

Daria E. Kim ◽

Joshua E. Zweig

Keyword(s):

Chemical Synthesis ◽

Total Synthesis ◽

Small Molecules ◽

First Principles ◽

Quantum Chemical ◽

Computational Analysis ◽

Empirical Evaluation ◽

Synthetic Strategy ◽

Catalyzed Reactions ◽

Enzyme Catalyzed Reactions

The diverse molecular architectures of terpene natural products are assembled by exquisite enzyme-catalyzed reactions. Successful recapitulation of these transformations using chemical synthesis is hard to predict from first principles and therefore challenging to execute. A means of evaluating the feasibility of such chemical reactions would greatly enable the development of concise syntheses of complex small molecules. Herein, we report the computational analysis of the energetic favorability of a key bio-inspired transformation, which we use to inform our synthetic strategy. This approach was applied to synthesize two constituents of the historically challenging indole diterpenoid class, resulting in a concise route to (–)-paspaline A in 9 steps from commercially available materials and the first pathway to and structural confirmation of emindole PB in 13 steps. This work highlights how traditional retrosynthetic design can be augmented with quantum chemical calculations to reveal energetically feasible synthetic disconnections, minimizing time-consuming and expensive empirical evaluation.

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Acids, bases and buffer solutions

10.1093/oso/9780198782957.003.0017 ◽

2018 ◽

Author(s):

Dennis Sherwood ◽

Paul Dalby

Keyword(s):

First Principles ◽

Buffer Capacity ◽

Unique Feature ◽

Dissociation Constants ◽

Equilibrium Composition ◽

Buffer Solutions ◽

Acid And Base ◽

Water Ph ◽

Acids And Bases ◽

Conjugate Bases

Many reactions in solution involve acids and bases, and so this chapter examines these important reactions in detail. Topics covered include the ionisation of water, pH, pOH, acids and bases, conjugate acids and conjugate bases, acid and base dissociation constants, the Henderson-Hasselbalch equation, the Henderson-Hasselbalch approximation, buffer solutions and buffer capacity. A unique feature of this chapter is a ‘first principles’ analysis of how a reaction buffered at a particular pH achieves an equilibrium composition different from that of the same reaction taking place in an unbuffered solution. This introduces some concepts which are important in understanding the biochemical standard state, as required for Chapter 23.

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Reactions in solution

10.1093/oso/9780198782957.003.0016 ◽

2018 ◽

Author(s):

Dennis Sherwood ◽

Paul Dalby

Keyword(s):

Phase Equilibria ◽

Gas Phase ◽

First Principles ◽

Unique Feature ◽

Life Sciences ◽

Equilibrium Mixture ◽

Second Law ◽

Ideal Solution ◽

Coupled Reactions ◽

Definition Of

Another key chapter, examining reactions in solution. Starting with the definition of an ideal solution, and then introducing Raoult’s law and Henry’s law, this chapter then draws on the results of Chapter 14 (gas phase equilibria) to derive the corresponding results for equilibria in an ideal solution. A unique feature of this chapter is the analysis of coupled reactions, once again using first principles to show how the coupling of an endergonic reaction to a suitable exergonic reaction results in an equilibrium mixture in which the products of the endergonic reaction are present in much higher quantity. This demonstrates how coupled reactions can cause entropy-reducing events to take place without breaking the Second Law, so setting the scene for the future chapters on applications of thermodynamics to the life sciences, especially chapter 24 on bioenergetics.

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