### Abstract

Modern quantum chemistry can make quantitative predictions on an immense array of chemical systems. However, the interpretation of those predictions is often complicated by the complex wave function expansions used. Here we show that an exceptionally simple algebraic construction allows for defining atomic core and valence orbitals, polarized by the molecular environment, which can exactly represent self-consistent field wave functions. This construction provides an unbiased and direct connection between quantum chemistry and empirical chemical concepts, and can be used, for example, to calculate the nature of bonding in molecules, in chemical terms, from first principles. In particular, we find consistency with electronegativities (χ), C 1s core-level shifts, resonance substituent parameters (σ_{R}), Lewis structures, and oxidation states of transition-metal complexes.

Original language | English (US) |
---|---|

Pages (from-to) | 4834-4843 |

Number of pages | 10 |

Journal | Journal of Chemical Theory and Computation |

Volume | 9 |

Issue number | 11 |

DOIs | |

State | Published - Nov 12 2013 |

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### All Science Journal Classification (ASJC) codes

- Computer Science Applications
- Physical and Theoretical Chemistry

### Cite this

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*Journal of Chemical Theory and Computation*, vol. 9, no. 11, pp. 4834-4843. https://doi.org/10.1021/ct400687b

**Intrinsic atomic orbitals : An unbiased bridge between quantum theory and chemical concepts.** / Knizia, Gerald.

Research output: Contribution to journal › Article

TY - JOUR

T1 - Intrinsic atomic orbitals

T2 - An unbiased bridge between quantum theory and chemical concepts

AU - Knizia, Gerald

PY - 2013/11/12

Y1 - 2013/11/12

N2 - Modern quantum chemistry can make quantitative predictions on an immense array of chemical systems. However, the interpretation of those predictions is often complicated by the complex wave function expansions used. Here we show that an exceptionally simple algebraic construction allows for defining atomic core and valence orbitals, polarized by the molecular environment, which can exactly represent self-consistent field wave functions. This construction provides an unbiased and direct connection between quantum chemistry and empirical chemical concepts, and can be used, for example, to calculate the nature of bonding in molecules, in chemical terms, from first principles. In particular, we find consistency with electronegativities (χ), C 1s core-level shifts, resonance substituent parameters (σR), Lewis structures, and oxidation states of transition-metal complexes.

AB - Modern quantum chemistry can make quantitative predictions on an immense array of chemical systems. However, the interpretation of those predictions is often complicated by the complex wave function expansions used. Here we show that an exceptionally simple algebraic construction allows for defining atomic core and valence orbitals, polarized by the molecular environment, which can exactly represent self-consistent field wave functions. This construction provides an unbiased and direct connection between quantum chemistry and empirical chemical concepts, and can be used, for example, to calculate the nature of bonding in molecules, in chemical terms, from first principles. In particular, we find consistency with electronegativities (χ), C 1s core-level shifts, resonance substituent parameters (σR), Lewis structures, and oxidation states of transition-metal complexes.

UR - http://www.scopus.com/inward/record.url?scp=84887852277&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84887852277&partnerID=8YFLogxK

U2 - 10.1021/ct400687b

DO - 10.1021/ct400687b

M3 - Article

VL - 9

SP - 4834

EP - 4843

JO - Journal of Chemical Theory and Computation

JF - Journal of Chemical Theory and Computation

SN - 1549-9618

IS - 11

ER -