Yes. You can create a Windows service that contains the logic for accessing the GSM modem and sending SMS messages. This service may be available from your ASP.NET web application.
There are many articles about starting a WCF service as a Windows service, here is one on MSDN, Hosting and Using WCF Services ,
But, on the other hand, the configuration of the service may be excessive. You can use your library from your application just as well.
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