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Question

The diatomic molecule HF has an absorption line in the rotational band at $40\text{ cm}^{-1}$ for the isotope $^{18}\text{F}$. The corresponding line for the isotope $^{19}\text{F}$ will be shifted by approximately

The correct answer is
$0.11\text{ cm}^{-1}$

Understanding Rotational Spectroscopy and Isotope Effects

The wavenumber ($\tilde{\nu}$) of rotational absorption lines in diatomic molecules is inversely proportional to the reduced mass ($\mu$) and the moment of inertia ($I$), which depends on the bond length ($r_0$). Specifically, for the $J=0 \to J=1$ transition, $\tilde{\nu} \propto B = \frac{h}{8\pi^2 c I} = \frac{h}{8\pi^2 c \mu r_0^2}$. Thus, $\tilde{\nu} \propto \frac{1}{\mu}$.

Calculating Reduced Masses

The reduced mass $\mu$ for a diatomic molecule AB is given by $\mu = \frac{m_A m_B}{m_A + m_B}$. We assume the mass of Hydrogen ($m_H$) is approximately 1 amu. The masses of the Fluorine isotopes are $m_{18F} \approx 18$ amu and $m_{19F} \approx 19$ amu.

  • For $^{18}\text{F}$: $\mu_{18} = \frac{m_H \cdot m_{18F}}{m_H + m_{18F}} = \frac{1 \times 18}{1 + 18} = \frac{18}{19} \text{ amu}$.
  • For $^{19}\text{F}$: $\mu_{19} = \frac{m_H \cdot m_{19F}}{m_H + m_{19F}} = \frac{1 \times 19}{1 + 19} = \frac{19}{20} \text{ amu}$.

Determining the Wavenumber Shift

Given that the absorption line for $^{18}\text{F}$ is at $\tilde{\nu}_{18} = 40\text{ cm}^{-1}$. Since $\tilde{\nu} \propto \frac{1}{\mu}$, we have:

$ \frac{\tilde{\nu}_{19}}{\tilde{\nu}_{18}} = \frac{\mu_{18}}{\mu_{19}} $

Substitute the values:

$ \frac{\tilde{\nu}_{19}}{40\text{ cm}^{-1}} = \frac{18/19}{19/20} = \frac{18}{19} \times \frac{20}{19} = \frac{360}{361} $

Now, calculate $\tilde{\nu}_{19}$:

$ \tilde{\nu}_{19} = 40 \times \frac{360}{361} = 40 \times \left(1 - \frac{1}{361}\right) \approx 40 - \frac{40}{361} \text{ cm}^{-1} $

The shift in wavenumber is:

$ \Delta\tilde{\nu} = |\tilde{\nu}_{18} - \tilde{\nu}_{19}| = \left| 40 - \left(40 - \frac{40}{361}\right) \right| = \frac{40}{361} \text{ cm}^{-1} $

Calculating the numerical value:

$ \Delta\tilde{\nu} \approx 0.1108 \text{ cm}^{-1} $

Therefore, the shift is approximately $0.11\text{ cm}^{-1}$.

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