Unravelling Chemical Interactions with Principal Interacting Orbital Analysis

Zhang, Jing‐Xuan; Sheong, Fu Kit; Lin, Zhenyang

doi:10.1002/chem.201801220

Cited by 166 publications

(162 citation statements)

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“…In this review, we are going to introduce the PIO analysis we recently developed, 49 which can on one hand complement the existing orbital-based methods when deciphering chemical bonding interactions, and on the other hand bridge the modern quantum chemical calculation results with chemists' intuitive thinking. We will first introduce the protocol and spirit of the PIO analysis, followed by giving both elementary and advanced examples to demonstrate how the PIO analysis captures fragment interactions in a sparse and compact manner while at the same time maintaining the chemical intuitiveness.…”

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confidence: 99%

Principal interacting orbital: A chemically intuitive method for deciphering bonding interaction

Zhang

Sheong

Lin

2020

WIREs Comput Mol Sci

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Modular bonding picture is a central part of chemical understanding as exemplified by the wide usage of Lewis structure as a chemical language to describe molecular electronic structures. A chemically intuitive bonding picture requires the descriptors to be localized and transferable. Molecular orbitals directly derived from quantum calculations are too delocalized to interpret in this regard, hence many efforts have been devoted to the development of bonding analysis methods. After a brief overview of various bonding analysis methods, this review outlines the framework of principal interacting orbital (PIO) analysis and presents its role in recovering intuitive chemical concepts and producing modular bonding pictures. The PIO analysis identifies the most important fragment orbitals that are involved in fragment interactions and characterizes a one-to-one orbital interaction pattern that underlies a unique set of bonding and anti-bonding orbitals derived from pairwise orbital interactions between two fragments. By making use of the principal component analysis (PCA), PIO analysis can effectively combine complex delocalized interaction patterns involved in numerous molecular orbitals into a handful of localized PIOs to provide easily interpretable results with intimate connection to localized chemical concepts, while maintaining necessary delocalized features when dealing with systems that involve mutlicentered interactions such as cluster compounds and various reactions. Such adaptability guarantees the robustness of PIO analysis with respect to change of substituents and the transferability of obtained PIOs across different systems. This article is categorized under: Structure and Mechanism > Molecular Structures K E Y W O R D S bonding theory, electronic structure, orbital interaction, principal interacting orbital 1 | INTRODUCTION Understanding chemical bonds and other chemical interactions is an elementary yet essential practice in chemistry and is fundamentally important when one tries to understand molecular geometric features and electronic properties. Long Jing-Xuan Zhang and Fu Kit Sheong contributed equally to this work. The code for PIO analysis is freely available at github.com/jxzhangcc/PIO.

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Principal interacting orbital: A chemically intuitive method for deciphering bonding interaction

Zhang

Sheong

Lin

2020

WIREs Comput Mol Sci

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“…To gain further understanding of why the key hexagon is essential for the stability of Ti(BN) n complexes, we have analyzed orbital interactions between the metal and the cage, based on the maximum bonding fragment orbital approach 35,36 . Figure 3 presents the orbital correlation diagram for the lowest energy complex, Ti & 2, revealing four principal metal-cage bonding interactions (each with a Wiberg bond order 37 greater than 0.5).…”

Section: Structural and Bonding Features Of Stable Ti(bn) 19 Isomersmentioning

confidence: 99%

“…Experimentally, BN cages containing a single metal atom have been produced by arc-melting synthesis, where the formation of Fe(BN) 36 24 , La(BN) 36 25 and Y(BN) n (n = 36, 37, 48) 11 species was confirmed by mass spectrometry and high-resolution electron microscopy. However, due to lack of crystal structure determination, the unambiguous, atomically resolved structures of metal-doped BN fullerenes still remain unclear.…”

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“…Orbital correlation diagram unraveling the nature of the metal-cage bonding in Ti & 2. The analysis is based on the maximum bonding fragment orbital approach35,36 . Each of the Ti's atomic orbitals (left panel) is paired up with one of the cage's fragment orbitals (right panel), leading to a pair of bonding and anti-bonding orbitals of the complex (middle panel).…”

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Modification of boron nitride nanocages by titanium doping results unexpectedly in exohedral complexes

Wang

2019

Nat Commun

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Despite their early experimental production and observation, the unambiguous molecular structures of metal-containing boron nitride (BN) nanocages still remain mysterious. It has been commonly assumed that this family of compounds has the metal atom confined inside the cage, just like their isoelectronic cousins, carbon metallofullerenes do. Here, we demonstrate that Ti(BN) n (n = 12-24) complexes have, unexpectedly, an exohedral structure instead of an endohedral one, which could be verified by collision-induced dissociation experiments. The predicted global minimum structures exhibit some common bonding features accounting for their high stability, and could be readily synthesized under typical conditions for generating BN nanoclusters. The Ti doping dramatically changes not only the cage topology, but the arrangement of B and N atoms, endowing the resultant compounds with potential for CO 2 capture and nitrogen fixation. These findings may expand or alter the understanding of BN nanostructures functionalized with other transition metals.

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“…To understand the electronic structure of the water octamer, we have analyzed the hydrogen-bond (HB) network of the cubic isomers using delocalized and localized molecular orbital theory. Theoretical approaches were applied of natural bond orbital (NBO) 34 , adaptive natural density partitioning (AdNDP) 35 , energy decomposition analysis-natural orbitals for chemical valence (EDA-NOCV) 36 , and principal interacting orbital (PIO) analysis 37 . Hydrogen bonding between an O-H antibonding orbital (denoted σ*(O−H)) and an adjacent oxygen lonepair (LP) donor can be viewed as a three-center two-electron (3c-2e) interaction, which features the O lone-pair delocalizing to the H−O antibonding region (Fig.…”

Section: Introductionmentioning

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Infrared spectroscopic study of hydrogen bonding topologies in the water octamer: The smallest ice cube

Zhang

et al. 2020

Preprint

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The water octamer, with its cubic structure consisting of six four-membered rings, presents an excellent system in which to unravel the cooperative interactions driven by subtle changes in the hydrogen-bonding topology. Although many distinct structures are calculated to exist, it has not been possible to extract the structural information encoded in their vibrational spectra because this requires size-selectivity of the neutral clusters with sufficient resolution to identify the contributions of the different isomeric forms. Here we report the size-specific infrared spectra of the isolated cold, neutral water octamer using a scheme based on threshold photoionization using a tunable vacuum ultraviolet free electron laser. A plethora of sharp vibrational bands features are observed for the first time. Theoretical analysis of these patterns reveals the coexistence of five cubic isomers, including two with chirality. The relative energies of these structures are found to reflect topology-dependent, delocalized multi-center hydrogen-bonding interactions. These results demonstrate that even with a common structural motif, the degree of cooperativity among the hydrogen-bonding network creates a hierarchy of distinct species. The implications of these results on possible metastable forms of ice are considered.

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Unravelling Chemical Interactions with Principal Interacting Orbital Analysis

Cited by 166 publications

References 50 publications

Principal interacting orbital: A chemically intuitive method for deciphering bonding interaction

Principal interacting orbital: A chemically intuitive method for deciphering bonding interaction

Modification of boron nitride nanocages by titanium doping results unexpectedly in exohedral complexes

Infrared spectroscopic study of hydrogen bonding topologies in the water octamer: The smallest ice cube

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