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The intervening low-frequency doorway modes play a key role in this process, yet their ultrafast dynamics remain largely unexplored due to the lack of experimental access. Here, we overcome this limitation using time-resolved ultrabroadband far-to-mid-infrared spectroscopy, which allows us to directly monitor vibrational energy transfer (VET) involving doorway and lattice modes across the full 100\u20131700\u00a0cm\u22121 range in crystalline \u03b2-HMX\u2014a spectral window inaccessible to conventional mid-infrared techniques. This broad range reveals a complete three-stage energy flow pathway: sub-picosecond vibrational energy redistribution among high-frequency modes, a 2\u201325\u00a0ps multi-stage VET network (vibrational \u2192 doorway \u2192 lattice), and final \u223c140\u00a0ps thermalization. Doorway-mode-mediated pathways govern VET, with an efficient route from NO2 symmetric stretch (\u03bd20) to short-lived doorway modes (\u03bd8\u2013\u03bd10, N\u2013NO2 in-plane bend) and then to the lattice. These results provide the first direct experimental validation of the doorway mechanism in an energetic molecular crystal and demonstrate the unique power of ultrabroadband infrared spectroscopy for revealing previously hidden vibrational channels.<\/jats:p>","DOI":"10.1063\/5.0337198","type":"journal-article","created":{"date-parts":[[2026,6,25]],"date-time":"2026-06-25T11:14:08Z","timestamp":1782386048000},"update-policy":"https:\/\/doi.org\/10.1063\/aip-crossmark-policy-page","source":"Crossref","is-referenced-by-count":0,"title":["Time-resolved ultrabroadband far-to-mid-infrared spectroscopy directly reveals doorway-mediated vibrational energy flow in an energetic crystal (\u03b2-HMX)"],"prefix":"10.1063","volume":"164","author":[{"ORCID":"https:\/\/orcid.org\/0000-0003-2302-3929","authenticated-orcid":false,"given":"Gangbei","family":"Zhu","sequence":"first","affiliation":[{"name":"National Key Laboratory of Shock Wave and Detonation Physics, Institute of Fluid Physics, China Academy of Engineering Physics , Mianyang 621900,","place":["People\u2019s Republic of China"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0009-0008-2123-8129","authenticated-orcid":false,"given":"Yangyang","family":"Zeng","sequence":"additional","affiliation":[{"name":"National Key Laboratory of Shock Wave and Detonation Physics, Institute of Fluid Physics, China Academy of Engineering Physics , Mianyang 621900,","place":["People\u2019s Republic of China"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-2932-8507","authenticated-orcid":false,"given":"Zhaoyang","family":"Zheng","sequence":"additional","affiliation":[{"name":"National Key Laboratory of Shock Wave and Detonation Physics, Institute of Fluid Physics, China Academy of Engineering Physics , Mianyang 621900,","place":["People\u2019s Republic of China"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Guoyang","family":"Yu","sequence":"additional","affiliation":[{"name":"National Key Laboratory of Shock Wave and Detonation Physics, Institute of Fluid Physics, China Academy of Engineering Physics , Mianyang 621900,","place":["People\u2019s Republic of China"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Yanqiang","family":"Yang","sequence":"additional","affiliation":[{"name":"National Key Laboratory of Shock Wave and Detonation Physics, Institute of Fluid Physics, China Academy of Engineering Physics , Mianyang 621900,","place":["People\u2019s Republic of China"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"317","published-online":{"date-parts":[[2026,6,25]]},"reference":[{"key":"2026062507140012300_c1","doi-asserted-by":"publisher","first-page":"9102","DOI":"10.1021\/j100022a023","article-title":"Ultrafast mode-specific intermolecular vibrational energy transfer to liquid nitromethane","volume":"99","year":"1995","journal-title":"J.\u00a0Phys. 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