Table 1 Cavity vibrational self-consistent field/configuration interaction (cav-VSCF/VCI) state energies and leading vibrational configuration interaction (VCI) coefficient(s) under different values of the light–matter coupling factor g with the cavity mode polarized along the O-O axis

From: Manipulating hydrogen bond dissociation rates and mechanisms in water dimer through vibrational strong coupling

Cavity mode frequency ω = 3547 cm−1

Coupling factor g

0.00

0.001

0.002

Energy (cm−1)

3547

3547a

3716

3531b

3563c

3717

3514b

3579c

3717

VCI coeff (cavity)

/

1.0

/

0.71

0.70

0.04

0.71

0.70

0.09

VCI coeff (HB str)

0.97

/

0.09

0.68

0.69

0.09

0.67

0.70

0.08

VCI coeff (free str)

0.16

/

0.99

0.09

0.05

0.99

0.11

0.04

0.98

VCI coeff (sym str)

/

/

/

/

0.05

/

/

0.06

/

VCI coeff (bend overtoned)

0.15

/

0.05

0.11

0.11

0.05

0.11

0.10

0.05

Coupling factor g

0.005

0.008

0.01

Energy (cm−1)

3466b

3623c

3724

3418b

3658c

3743

3386b

3671c

3766

VCI coeff (cavity)

0.72

0.68

0.22

0.72

0.54

0.42

0.72

0.44

0.52

VCI coeff (HB str)

0.66

0.72

0.02

0.64

0.69

0.21

0.63

0.65

0.35

VCI coeff (free str)

0.15

0.16

0.96

0.18

0.43

0.87

0.20

0.59

0.77

VCI coeff (sym str)

/

0.05

/

/

0.16

/

/

0.18

/

VCI coeff (bend overtoned)

0.13

0.10

0.04

0.15

0.11

0.01

0.17

0.11

<0.01

  1. “/” indicates the VCI coefficients smaller than 0.005. “HB str”, “free str”, and “sym str” indicate the hydrogen bonded OH stretch, free OH stretch, and symmetric OH stretch respectively.
  2. aFundamental frequency of the cavity mode.
  3. bLower polariton state (LP).
  4. cUpper polariton state (UP).
  5. dBend overtone of the donor water.
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